Substituted 5-aryl-2-(2-hydroxyphenyl)-2h-benzotriazole UV absorbers, compositions stabilized therewith and process for preparation thereof

ABSTRACT

where R is an aryl moiety, such as phenyl, naphthyl or biphenylyl, or is phenyl substituted by one or more trifluoromethyl, bromo or cyano, and E 1  and E 2  are independently hydrogen, alkyl, aralkyl and the like are prepared by reaction of a benzotriazole substituted on the 5-position of the benzo ring by a halogen atom with a arylboronic acid or ester in the presence of a transition-metal catalyst, such as palladium (II) diacetate. The benzotriazole compounds of formula I are particularly efficacious as stabilizers for automotive coatings and candle wax.

[0001] The instant invention pertains to novel 5-aryl substitutedbenzotriazole UV absorbers, to a novel process for their preparation andto compositions stabilized by said benzotriazoles.

BACKGROUND OF THE INVENTION

[0002] The benzotriazoles have long been an important class of UVabsorbers and have gained wide commercial importance and acceptance formany industrial applications. The prior art is replete with referencesto their manufacture and utility. However, as requirements become evermore stringent and demanding, the search for still more stable anddurable benzotriazoles continues. The gradual phase out of HAPSsolvents, such as xylene, because of environmental concerns and theirreplacement with non-HAPS solvents, such as esters, ethers or ketones,and increased durability requirements for automotive coatings make thissearch more urgent. Indeed, the automotive industry is most concernedabout UVA losses from automotive paints and coatings as seen in thepublication by J. L. Gerlock et al., Proc. 36th Annual Tech. Sym.(Cleveland Coating Society), May 18, 1993.

[0003] U.S. Pat. Nos. 4,226,763; 4,278,589; 4,315,848; 4,275,004;4,347,180; 5,554,760; 5,563,242; 5,574,166 and 5,607,987 describeselected benzotriazoles, substituted in the 3-position of thehydroxyphenyl ring by an α-cumyl group, which show very good durabilityin automotive coatings. These benzotriazoles represent the present stateof the art. The instant invention is directed at preparingbenzotriazoles which exhibit still better durability and low loss ratesfrom the prior art benzotriazoles.

[0004] U.S. Pat. Nos. 5,278,314; 5,280,124; 5,436,349 and 5,516,914describe red-shifted benzotriazoles. These benzotriazoles aresubstituted in the 3-position of the phenyl ring with an α-cumyl groupand at the 5-position of the benzo ring by thio ethers, alkylsulfonyl orphenylsulfonyl moieties. Red-shifting the benzotriazoles is desirablefor spectral reasons. A group at the 5-position which is also electronwithdrawing provides additional benefits in low loss rates anddurability as found in the instant invention. Missing from these patentsare any alkylsulfones with seven or fewer carbon atoms. When suchsulfonyl substituents are combined with specifically α-cumyl moieties,extremely durable compounds result which, due to the bulk of the α-cumylmoiety have sufficiently low volatility to be useful in coating andother polymer systems.

[0005] The presence of an α-cumyl or phenyl group ortho to the hydroxygroup on the phenyl ring exerts a surprisingly large positive effect onbenzotriazole photostability in coatings and photographic gel systems.The magnitude of this effect, particularly when compared to a tert-butylgroup in that position, is well beyond prediction. The combination ofboth an electron withdrawing group on the benzo ring and an α-cumyl orphenyl group on the phenyl ring in the same molecule leads to extremelydesirable properties in coating systems when high UV absorber permanenceis critical.

[0006] Novel compounds meeting these parameters as being extremelystable in aggressive use environments constitute a first portion of thisinvention.

[0007] The presence of the electron withdrawing moiety at the 5-positionof the benzo ring has a powerful stabilizing effect on benzotriazoles ingeneral and is observed in other polymer systems such as polycarbonateand poly(vinyl chloride) substrates as well. However, the effect ofhaving an α-cumyl or phenyl group ortho to the hydroxy moiety on thephenyl ring is much smaller to non-existent in some polymer systems suchas polycarbonate or poly(vinyl chloride) even though critical forcoating systems as described above.

[0008] In addition to being more photostable, the compounds of thisinvention are red-shifted, absorbing strongly in the 350-400 nmwavelength range. While such red-shifting is desirable in that a greaterportion of the UV spectrum is absorbed, this can also introduce color ifthe absorption beyond 400 nm is significant. This can limit the use ofsuch compounds, particularly in systems such as polycarbonate glazingapplications or present difficulties in various pigmented systems.

[0009] It is found that the nature of the substituent ortho to thehydroxyl group on the phenyl ring has an unexpected impact on colorimparted to the substrate by the benzotriazole. Thus, relatively subtledifferences in substitution on the phenyl ring can have a large impacton the resulting color and the applicability of the benzotriazole inspecific color sensitive applications. There are striking differencesbetween having hydrogen, alkyl or α-cumyl at this 3-position.

[0010] Furthermore, U.S. Pat. No. 5,977,219 teaches that, when the5-position of the benzo ring is substituted with a trifluoromethylgroup, the resulting benzotriazole not only exhibits the same or greaterenhanced stability when incorporated into thermoplastic resins, but alsoimparts less color than related benzotriazoles substituted at the5-position with other electron withdrawing moieties such as sulfonyl orcarbonyl. These trifluoromethyl compounds also absorb strongly in the350-400 nm wavelength range despite the low color and are extremelycompatible in a wide range of substrates such as acrylic resins,hydrocarbons, polycarbonates and poly(vinyl chloride).

[0011] There are a multitude of general references to benzotriazoleshaving in the 5-position of the benzo ring electron withdrawing groupssuch as esters, amides, sulfones and the like that are not substitutedin the 3-position of the phenyl ring by an α-cumyl or phenyl moiety. Inmany of these references the broadly described compounds areunexemplified and no teaching or appreciation taught of the positiveeffect on photostability described in this invention. In any event, thevast majority of these structures fall well outside the scope of instantinvention.

[0012] Japanese 1996-299547 discloses the use of heterocyclic compoundsas non-aqueous electrolytes for lithium batteries. These heterocycliccompounds included benzotriazoles substituted on the benzo ring byhydrogen, methyl, ethyl, amino, hydroxyl, 2-pyridyl or phenyl; andsubstituted on the hydroxyphenyl ring by at the 5-position by a methylgroup and at the 3-position by hydrogen, methyl, ethyl, amino, hydroxyl,2-pyridyl or phenyl.

[0013] U.S. Pat. No. 4,396,712 describes generically benzotriazolecompounds which are substituted at the 5-position of the benzo ring byphenyl as light stabilizers for photothermographic film. The onlycompound disclosed specifically is5-phenyl-2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole. Thebenzotriazole UV absorbers provide improved storage stability bystabilizing the silver salts (oxidizing agents) in these dry imageforming materials. Only selected low molecular weight benzotriazoles aresuitable since the benzotriazole must be compatible with othercomponents of the image forming materials.

[0014] A. Suzuki, Pure & Applied Chem., 66, No. 2, 213 (1994) describesa new synthetic method involving the reaction of sterically hinderedaryl boronic acids or esters with sterically hindered haloarenes in thepresence of palladium (II) catalysts. This reaction has become known asthe Suzuki reaction.

[0015] B. E. Huff et al., Organic Synthesis, 75, 53 (1998) describe thesynthesis of unsymmetrical biaryls using a modified Suzukicross-coupling to form 4-biphenylcarbox-aldehyde.

[0016] J. P. Wolfe, et al., J. Am. Chem. Soc., 1999, 121, 9550 describethe use of highly active palladium catalysts for Suzuki couplingreactions.

[0017] WO 00/22037 describes the stabilization of solid, shaped andcolored wax articles using a malonate UV absorber which may besubstituted by a hindered amine group.

[0018] Japanese Hei 5-93164 discloses the use of benzotriazole UVabsorbers and hindered amines in stabilizing pigmented wax crayons.

[0019] Copending U.S. patent application Ser. Nos. 09/496,084;09/495,495 and 09/495,496 all describe the stabilization of candle waxusing other types of benzotriazole UV absorbers.

DETAILED DESCRIPTION

[0020] The instant invention pertains to compounds of formula I or II

[0021] wherein

[0022] R is phenyl, naphthyl, biphenylyl, 9-phenanthryl or said phenyl,naphthyl, biphenylyl or 9-phenanthryl substituted by one to three alkylof 1 to 18 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, R₃S—,R₃SO—, R₃SO₂, aryl of 6 to 10 carbon atoms, perfluoroalkyl of 1 to 12carbon atoms, halogen, nitro, cyano, carboxyl, alkoxycarbonyl of 2 to 19carbon atoms, hydroxyl, alkoxy of 1 to 18 carbon atoms, aryloxy of 6 to10 carbon atoms, aralkoxy of 7 to 15 carbon atoms, vinyl, acetyl,acetamido, amino, dialkylamino of 2 to 12 carbon atoms, formyl,thioalkoxy of 1 to 18 carbon atoms, hydroxymethyl, amino-methyl,halomethyl, sulfato, phosphato or where any two substituents form abenzo ring with the aryl moiety to which they are attached,

[0023] T is a direct bond, 1,4-phenylene or said phenylene substitutedby one or two alkyl of 1 to 12 carbon atoms,

[0024] R₃ is alkyl of 1 to 18 carbon atoms, phenylalkyl of 7 to 15carbon atoms or aryl of 6 to 10 carbon atoms,

[0025] E₁ is hydrogen, straight or branched alkyl of 1 to 24 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl orsaid phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to4 carbon atoms,

[0026] E₂ is straight or branched alkyl chain of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkylof 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or E₂ is alkyl of 1 to 24 carbon atoms oralkenyl of 2 to 18 carbon atoms substituted by one or more —OH, —OCOE₃,—NH₂, —NHCOE₃ or —COOE₃, or mixtures thereof; or said alkyl or saidalkenyl interrupted by one or more —O— which can be unsubstituted orsubstituted by one or more —OH groups; where E₃ is hydrogen or alkyl of1 to 24 carbon atoms, and where said alkyl is interrupted by one or more—O— and which can be substituted by one or more —OH or —OR₂₁ groupswhere R₂₁ is alkyl of 1 to 12 carbon atoms; and

[0027] with the proviso that5-phenyl-2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole isexcluded; and

[0028] with the further proviso that, when E₁ is hydrogen, methyl orethyl and E₂ is methyl or ethyl, R is not phenyl.

[0029] Another embodiment are the compounds of formula I are those whereR is phenyl, 2-naphthyl, 3-biphenylyl, 4-biphenylyl, 9-phenanthryl,2-trifluoromethylphenyl, 3-trifluoromethylphenyl,4-trifluoromethylphenyl, 3,5-ditrifluoromethylphenyl, 4-cyanophenyl,3-methylphenyl, 3-isopropylphenyl, 3-fluorophenyl, 3-chlorophenyl,3-bromophenyl, 3-iodophenyl, 3-methoxyphenyl, 3-ethoxyphenyl,3-benzyloxyphenyl, 3-hydroxyphenyl, 3-hydroxymethylphenyl,3-thiomethylphenyl, 3-bromomethylphenyl, 3-cyanophenyl, 3-vinylphenyl,3-acetylphenyl, 3-aminophenyl, 3-acetamidophenyl, 3-formylphenyl,3-isothiocyano-phenyl, 2-ethylphenyl, 2-cyanophenyl, 2-acetylphenyl,2-bromomethylphenyl, 2-bromophenyl, 2-vinylphenyl, 2-aminophenyl,2-hydroxyphenyl, 2-ethoxyphenyl, 2-fluorophenyl, 2-chlorophenyl,2-methoxyphenyl, 2-formylphenyl, 2-methylphenyl, 4-n-butylphenyl,4-n-nonylphenyl, 4-methoxycarbonylphenyl, 4-cyanomethylphenyl,4-aminomethylphenyl, 4-isobutylphenyl, 4-iodophenyl, 4-thioethylphenyl,4-bromomethylphenyl, 4-benzyloxyphenyl, 4-acetylphenyl,4-dimethylaminophenyl, 4-hydroxyphenyl, 4-isopropylphenyl,4-tert-butylphenyl, 4-amino-phenyl, 4-n-amylphenyl, 4-ethylphenyl,4-hydroxymethylphenyl, 4-ethoxyphenyl, 4-vinylphenyl, 4-formylphenyl,4-carboxyphenyl, 4-thiomethylphenyl, 4-phenoxyphenyl, 4-methoxy-phenyl,4-methylphenyl, 4-chlorophenyl, 4-fluorophenyl, 4-bromophenyl,2,6-dimethylphenyl, 3,5-ichlorophenyl, 3,5-dimethylphenyl,3,5-dibromophenyl, 3,5-difluorophenyl, 3-chloro-4-fluorophenyl,3,4-difluorophenyl, 3-amino-4-methylphenyl, 3,4-dichlorophenyl,3-hydroxy-4-methylphenyl, 3-amino-4-methylphenyl, 3-fluoro-4-bromophenylor 3-fluoro-4-formyl-phenyl, and where E₁ and E₂ are independentlystraight or branched chain alkyl of 4 to 24 carbon atoms or phenylalkylof 7 to 15 carbon atoms, or E₁ is additionally phenyl.

[0030] Another embodiment of the instant invention are compounds offormula II where T is a direct bond, 1,4-phenylene or2,5-di-n-hexyl-1,4-phenyene and where E₁ and E₂ are independently astraight or branched chain alkyl of 4 to 24 carbon atoms or phenylalkylof 7 to 15 carbon atoms.

[0031] Another embodiment of the instant invention are the compounds offormula I or II where R is phenyl, 2-trifluoromethylphenyl,3-trifluoromethylphenyl, 4-trifluoromethylphenyl,3,5-di-trifluoromethylphenyl, 4-cyanophenyl, 4-methoxyphenyl or1,1′biphenyl-4-ylphenyl, T is 1,4-phenylene, E₁ is phenyl or α-cumyl,and E₂ is tert-butyl or tert-octyl.

[0032] Still another embodiment of the instant invention are compoundsof formula I where R is phenyl or 4-trifluoromethylphenyl; E₁ isα-cumyl; and E₂ is tert-octyl.

[0033] The instant invention also pertains to the method of making theinstant compounds of formula I or II

[0034] where R, T, E₁ and E₂ are as defined above,

[0035] by the reaction of an arylboronic acid or ester of formula III orIV

R—B(OR₁)(OR₂)  (III)

(R₂O)(R₁O)B-T-B(OR₁)(OR₂)  (IV)

[0036] where R₁ and R₂ are independently hydrogen, alkyl of 1 to 12carbon atoms, or R₁ and R₂ together are alkylene of 2 to 4 carbon atoms;

[0037] with a 5-substituted benzotriazole of formula V

[0038] where X is chloro, bromo or iodo, or tosylate, in the presence ofan effective amount of a palladium (II) catalyst and optionally in theadditional presence of a ligand, such as triphenylphosphine, at atemperature between 10 to 100° C., preferably between 50 to 95° C.

[0039] When a ligand is used, the ligand is triphenylphosphine,2-(di-tert-butyl-phosphino)biphenyl,1,1′-bis[2,4,8,10-tetrakis(tert-butyl)-dibenzo[d,f][1,3,2]dioxa-phosphepin-6-yl]ferrocene,tris(2,4-di-tert-butylphenyl) phosphite or2,2′,2″-nitrilo-[triethyl-tris(3,3′,5,5′-tetra-tert-butyl-1,1′biphenyl-2,2′-diyl)phosphite].In another embodiment, the ligand is triphenylphosphine.

[0040] Preferably the amount of palladium (II) catalyst is 0.01 to 10mol percent.

[0041] In one embodiment of the invention, an anhydrous process is usedwith dioxane as solvent and potassium fluoride as a base; or the processcan be run using n-propanol or isopropanol as solvent with a smallamount of water and aqueous sodium carbonate as a base.

[0042] When any of R₁ to R₃ or any of E₁ to E₃ is alkyl, such groupsare, straight or branched chain, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl,n-octyl, 2-ethylhexyl, tert-octyl, lauryl, undecyl, tert-dodecyl,tridecyl, n-hexadecyl, n-octadecyl and eicosyl; when any of saidradicals is alkenyl, such groups are, for example, allyl, methallyl.2-n-hexenyl, 4-n-octenyl or oleyl; when any of said radicals iscycloalkyl, such groups are, for example, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl or cyclododecyl; when any of said radicals arephenylalkyl, such groups are, for example, benzyl, α-phenethyl,2-phenethyl, α-methylbenzyl or α,α-dimethylbenzyl; and when any of saidradicals is aryl, they are, for example, phenyl, α-naphthyl orβ-naphthyl or when substituted by alkyl are, for example, tolyl andxylyl. When alkyl is substituted by one or more —O— groups and/orsubstituted by one or more —OH, these groups can be hydroxymethyl,2-hydroxyethyl or 2-hydroxypropyl or can be, for example,—(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OR₂₁ where w is 1 to 12 and R₂₁ isalkyl of 1 to 12 carbon atoms; when any of said radicals is halogen,they are, for example, fluoro, chloro, bromo or iodo; when any of saidradicals is alkoxycarbonyl, they are, for example, methoxycarbonyl,ethoxycarbonyl, butoxycarbonyl, hexyloxycarbonyl, octyloxycarbonyl, ordodecyloxycarbonyl; when any of said radicals is alkoxy or aryloxy, theyare, for example, the same alkyl or same aryl definition as seen above.

[0043] The instant invention also pertains to a composition stabilizedagainst thermal, oxidative or light-induced degradation which comprises,

[0044] (a) an organic material subject to thermal, oxidative orlight-induced degradation, and

[0045] (b) an effective stabilizing amount of a compound of formula I orII

[0046] wherein

[0047] R is phenyl, naphthyl, biphenylyl, 9-phenanthryl or said phenyl,naphthyl, biphenylyl or 9-phenanthryl substituted by one to three alkylof 1 to 18 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, R₃S—,R₃SO—, R₃SO₂, aryl of 6 to 10 carbon atoms, perfluoroalkyl of 1 to 12carbon atoms, halogen, nitro, cyano, carboxyl, alkoxycarbonyl of 2 to 19carbon atoms, hydroxyl, alkoxy of 1 to 18 carbon atoms, aryloxy of 6 to10 carbon atoms, aralkoxy of 7 to 15 carbon atoms, vinyl, acetyl,acetamido, amino, dialkylamino of 2 to 12 carbon atoms, formyl,thioalkoxy of 1 to 18 carbon atoms, hydroxymethyl, amino-methyl,halomethyl, sulfato, phosphato or where any two substituents form abenzo ring with the aryl moiety to which they are attached,

[0048] T is a direct bond, 1,4-phenylene or said phenylene substitutedby one or two alkyl of 1 to 12 carbon atoms,

[0049] R₃ is alkyl of 1 to 18 carbon atoms, phenylalkyl of 7 to 15carbon atoms or aryl of 6 to 10 carbon atoms,

[0050] E₁ is hydrogen, straight or branched alkyl of 1 to 24 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl orsaid phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to4 carbon atoms,

[0051] E₂ is straight or branched alkyl chain of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkylof 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or E₂ is alkyl of 1 to 24 carbon atoms oralkenyl of 2 to 18 carbon atoms substituted by one or more —OH, —OCOE₃,—NH₂, —NHCOE₃ or —COOE₃, or mixtures thereof; or said alkyl or saidalkenyl interrupted by one or more —O— which can be unsubstituted orsubstituted by one or more —OH groups; where E₃ is hydrogen or alkyl of1 to 24 carbon atoms, and where said alkyl is interrupted by one or more—O— and which can be substituted by one or more —OH or —OR₂₁ groupswhere R₂₁ is alkyl of 1 to 12 carbon atoms.

[0052] The organic material is a natural, semi-synthetic or syntheticpolymer, such as a thermoplastic polymer.

[0053] In other embodiments, the polymer is a polyolefin orpolycarbonate, such as polyethylene or polypropylene; or polypropylene;or the polymer is a styrenic, ABS, a nylon, a polyester such aspoly(ethylene terephthalate) or poly(butylene terephthalate), apolyurethane, an acrylate, a rubber modified styrenic, poly(vinylchloride), poly(vinyl butyral), polyacetal (polyoxymethylene),poly(ethylene naphthalenedicarboxylate), or other blends or copolymerssuch as poly(ethylene/1,4-cyclohexylenedimethylene terephthalate) PETGor an ionomer.

[0054] In another embodiment of the instant invention, the organicmaterial is a resin selected from the group consisting of a thermosetacrylic melamine resin, an acrylic urethane resin, an epoxy carboxyresin, a silane modified acrylic melamine, an acrylic resin withcarbamate pendant groups crosslinked with melamine or an acrylic polyolresin crosslinked with melamine containing carbamate groups.

[0055] In still other embodiments, the resin is a thermoset acrylicmelamine resin or an acrylic urethane resin.

[0056] In yet another embodiment of the instant invention, the organicmaterial is a recording material.

[0057] The recording materials according to the invention are suitablefor pressure-sensitive copying systems, photocopying systems usingmicrocapsules, heat-sensitive copying systems, photographic materialsand ink jet printing.

[0058] The recording materials according to the invention aredistinguished by an unexpected improvement in quality, especially withregard to the fastness to light.

[0059] The recording materials according to the invention have theconstruction known for the particular use. They consist of a customarycarrier, for example, paper or plastic film, which has been coated withone or more layers. Depending on the type of material, these layerscontain the appropriate necessary components, in the case ofphotographic materials, for example, silver halide emulsions, dyecouplers, dyes and the like. Material particularly suitable for ink jetprinting has a layer particularly absorptive for ink on a customarycarrier. Uncoated paper can also be employed for ink jet printing. Inthis case the paper acts at the same time as the carrier material and asthe ink-absorbent layer. Suitable material for ink jet printing is, forexample, described in U.S. Pat. No. 5,073,448 which is incorporatedherein by reference.

[0060] The recording material can also be transparent as, for example,in the case of projection films.

[0061] The compounds of formula I or II can be incorporated into thecarder material as early as the production of the latter, in theproduction of paper, for example, being added to the paper pulp. Asecond method of application is to spray the carder material with anaqueous solution of compounds of formula I or II or to add the compoundsto the coating composition.

[0062] Coating compositions intended for transparent recording materialssuitable for projection cannot contain any particles which scatterlight, such as pigments and fillers.

[0063] The dye-binding coating composition can contain a number of otheradditives, for example, antioxidants, light stabilizers (including alsoUV absorbers which do not fall under the scope of the UV absorbers ofthis invention), viscosity improvers, fluorescent brighteners, biocidesand/or antistatic agents.

[0064] The coating composition is usually prepared as follows: thewater-soluble components, for example, the binder, are dissolved inwater and stirred together; the solid components, for example, fillersand other additives already described, are dispersed in this aqueousmedium; and disperison is advantageously carried out by means ofdevices, for example, ultrasonic systems, turbine stirrers,homogenizers, colloid mills, bead mills, sand mills, high-speed stirrersand the like. The compounds of formula I or II can be easilyincorporated into the coating composition.

[0065] The recording material according to this invention preferablycontains 1 to 5000 mg/m², in particular 50-1200 mg/m², of a compound offormula I or II.

[0066] As already mentioned, the recording materials according to theinvention embrace a wide field. The compounds of formula I or II can,for example, be employed in pressure-sensitive copying systems. They canbe introduced either into the paper in order to protect themicroencapsulated dye precursors there from light, or into the binder ofthe developer layer in order to protect the dyes formed there.

[0067] Photocopying systems using light-sensitive microcapsules whichare developed by means of pressure are described in U.S. Pat. Nos.4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,535,463; 4,551,407;4,562,137 and 4,608,330; and also in EP-A 139,479; EP-A 162,664; EP-A164,931; EP-A 237,024; EP-A 237,025 and EP-A 260,129. In all thesesystems, the compounds can be put into the dye-receiving layer. Thecompounds can, however, also be put into the donor layer in order toprotect the color formers from light.

[0068] Photographic materials which can be stabilized are photographicdyes and layers containing such dyes or precursors thereof, for example,photographic paper and films. Suitable materials are, for example,described in U.S. Pat. No. 5,364,749 which is incorporated herein byreference. The compounds of formula I or II act here as a UV filteragainst electrostatic flashes. In color photographic materials, couplersand dyes are also protected against photochemical decomposition.

[0069] The instant compounds can be used for all types of colorphotographic materials. For example, they can be employed for colorpaper, color reversal paper, direct-positive color material, colornegative film, color positive film, color reversal film and the like.They are preferably used inter alia for photographic color materialwhich contains a reversal substrate or form positives.

[0070] Color-photographic recording materials usually contain, on asupport, a blue-sensitive and/or a green-sensitive and/or ared-sensitive silver halide emulsion layer and, if desired, a protectionlayer, with the instant compounds being, preferably, either in thegreen-sensitive or the red-sensitive layer or in a layer between thegreen-sensitive and the red-sensitive layer or in a layer on top of thesilver halide emulsion layers.

[0071] The compounds of formula I or II can also be employed inrecording materials based on the principles of photopolymerization,photoplasticization or the rupture of microcapsules, or in cases whereheat-sensitive and light-sensitive diazonium salts, leuko dyes having anoxidizing agent or dye lactones having Lewis acids are used.

[0072] Furthermore, the instant compounds can be employed in recordingmaterials for dye diffusion transfer printing, thermal wax transferprinting and non-matrix printing and for use with electrostatic,electrographic, electrophoretic, magnetographic andlaser-electrophotographic printers and pen-plotters. Of the above,recording materials for dye diffusion transfer printing are preferred,for example, as described in EP-A 507,734.

[0073] The instant compounds can also be employed in inks, such as forink jet printing, for example, as described in U.S. Pat. No. 5,098,477which is incorporated herein by reference.

[0074] The instant compounds also are effective in the protection ofdyes present in candle wax from premature degradation and fading.

[0075] The instant compounds of formula I or II are also useful inadhesives used in solar films, optical films and other laminatedstructures against the adverse effects of ultraviolet light and actinicradiation.

[0076] The compounds of this invention exhibit superior hydrolyticstability, handling and storage stability as well as good resistance toextractability when present in a stabilized composition.

[0077] The methodology to make the instant compounds is described in theprior art. The intermediates needed to make the instant compounds arelargely items of commerce.

[0078] In general polymers which can be stabilized include

[0079] 1. Polymers of monoolefins and diolefins, for examplepolypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forinstance of cyclopentene or norbornene, polyethylene (which optionallycan be crosslinked), for example high density polyethylene (HDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),branched low density polyethylene (BLDPE). Polyolefins, i.e. thepolymers of monoolefins exemplified in the preceding paragraph,preferably polyethylene and polypropylene, can be prepared by different,and especially by the following, methods:

[0080] a) radical polymerisation (normally under high pressure and atelevated temperature).

[0081] b) catalytic polymerisation using a catalyst that normallycontains one or more than one metal of groups IVb, Vb, VIb or VIII ofthe Periodic Table. These metals usually have one or more than oneligand, typically oxides, halides, alcoholates, esters, ethers, amines,alkyls, alkenyls and/or aryls that may be either μ- or σ-coordinated.These metal complexes may be in the free form or fixed on substrates,typically on activated magnesium chloride, titanium(III) chloride,alumina or silicon oxide. These catalysts may be soluble or insoluble inthe polymerisation medium. The catalysts can be used by themselves inthe polymerisation or further activators may be used, typically metalalkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metalalkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa ofthe Periodic Table. The activators may be modified conveniently withfurther ester, ether, amine or silyl ether groups. These catalystsystems are usually termed Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0082] 2. Mixtures of the polymers mentioned under 1), for examplemixtures of polypropylene with polyisobutylene, polypropylene withpolyethylene (for example PP/HDPE, PP/LDPE) and mixtures of differenttypes of polyethylene (for example LDPE/HDPE).

[0083] 3. Copolymers of monoolefins and diolefins with each other orwith other vinyl monomers, for example ethylene/propylene copolymers,linear low density polyethylene (LLDPE) and mixtures thereof with lowdensity polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/-isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

[0084] 4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

[0085] 5. Polystyrene, poly(α-methylstyrene), poly(α-methylstyrene).

[0086] 6. Copolymers of styrene or α-methylstyrene with dienes oracrylic derivatives, for example styrene/butadiene,styrene/acrylonitrile, styrene/alkyl methacrylate,styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate,styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength of styrene copolymers and anotherpolymer, for example a polyacrylate, a diene polymer or anethylene/-propylene/diene terpolymer, and block copolymers of styrenesuch as styrene/butadiene/-styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene orstyrene/ethylene/-propylene/styrene.

[0087] 7. Graft copolymers of styrene or α-methylstyrene, for examplestyrene on polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

[0088] 8. Halogen-containing polymers such as polychloroprene,chlorinated rubbers, chlorinated PVC, chlorinated or sulfochlorinatedpolyethylene, copolymers of ethylene and chlorinated ethylene,epichlorohydrin homo- and copolymers, especially polymers ofhalogen-containing vinyl compounds, for example polyvinyl chloride,polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, aswell as copolymers thereof such as vinyl chloride/vinylidene chloride,vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetatecopolymers.

[0089] 9. Polymers derived from α,β-unsaturated acids and derivativesthereof such as polyacrylates and polymethacrylates; polymethylmethacrylates, polyacrylamides and polyacrylo-nitriles, impact-modifiedwith butyl acrylate.

[0090] 10. Copolymers of the monomers mentioned under 9) with each otheror with other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

[0091] 11. Polymers derived from unsaturated alcohols and amines or theacyl derivatives or acetals thereof, for example polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;as well as their copolymers with olefins mentioned in 1) above.

[0092] 12. Homopolymers and copolymers of cyclic ethers such aspolyalkylene glycols, polyethylene oxide, polypropylene oxide orcopolymers thereof with bisglycidyl ethers.

[0093] 13. Polyacetals such as polyoxymethylene and thosepolyoxymethylenes which contain ethylene oxide as a comonomer,polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

[0094] 14. Polyphenylene oxides and sulfides, and mixtures ofpolyphenylene oxides with styrene polymers or polyamides.

[0095] 15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

[0096] 16. Polyamides and copolyamides derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, for example polyamide 4, polyamide 6, polyamide6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromaticpolyamides starting from m-xylene diamine and adipic acid; polyamidesprepared from hexamethylenediamine and isophthalic or/and terephthalicacid and with or, without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

[0097] 17. Polyureas, polyimides, polyamide-imides andpolybenzimidazoles.

[0098] 18. Polyesters derived from dicarboxylic acids and diols and/orfrom hydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

[0099] 19. Polycarbonates and polyester carbonates.

[0100] 20. Polysulfones, polyether sulfones and polyether ketones.

[0101] 21. Crosslinked polymers derived from aldehydes on the one handand phenols, ureas and melamines on the other hand, such asphenolformaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

[0102] 22. Drying and non-drying alkyd resins.

[0103] 23. Unsaturated polyester resins derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

[0104] 24. Crosslinkable acrylic resins derived from substitutedacrylates, for example epoxy acrylates, urethane acrylates or polyesteracrylates.

[0105] 25. Alkyd resins, polyester resins and acrylate resinscrosslinked with melamine resins, urea resins, polyisocyanates or epoxyresins.

[0106] 26. Crosslinked epoxy resins derived from polyepoxides, forexample from bisglycidyl ethers or from cycloaliphatic diepoxides.

[0107] 27. Natural polymers such as cellulose, rubber, gelatin andchemically modified homologous derivatives thereof, for examplecellulose acetates, cellulose propionates and cellulose butyrates, orthe cellulose ethers such as methyl cellulose; as well as rosins andtheir derivatives.

[0108] 28. Blends of the aforementioned polymers (polyblends), forexample PP/EPDM, Poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.

[0109] 29. Naturally occurring and synthetic organic materials which arepure monomeric compounds or mixtures of such compounds, for examplemineral oils, animal and vegetable fats, oil and waxes, or oils, fatsand waxes based on synthetic esters (e.g. phthalates, adipates,phosphates or trimellitates) and also mixtures of synthetic esters withmineral oils in any weight ratios, typically those used as spinningcompositions, as well as aqueous emulsions of such materials.

[0110] 30. Aqueous emulsions of natural or synthetic rubber, e.g.natural latex or latices of carboxylated styrene/butadiene copolymers.

[0111] 31. Polysiloxanes such as the soft, hydrophilic polysiloxanesdescribed, for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

[0112] 32. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

[0113] 33. Radiation curable compositions containing ethylenicallyunsaturated monomers or oligomers and a polyunsaturated aliphaticoligomer.

[0114] 34. Epoxymelamine resins such as light-stable epoxy resinscrosslinked by an epoxy functional coetherified high solids melamineresin such as LSE-4103 (Monsanto).

[0115] In general, the compounds of the present invention are employedin from about 0.01 to about 5% by weight of the stabilized composition,although this will vary with the particular substrate and application.An advantageous range is from about 0.05 to about 3%, and especially0.05 to about 1%. However, some high performance films or in UVabsorbing layers of laminates such as those produced by coextrusion maycontain from 5-15% by weight of the instant compounds. Concentrations of5-10% by weight are typical in certain coextrusion applications.

[0116] The stabilizers of the instant invention may readily beincorporated into the organic polymers by conventional techniques, atany convenient stage prior to the manufacture of shaped articlestherefrom. For example, the stabilizer may be mixed with the polymer indry powder form, or a suspension or emulsion of the stabilizer may bemixed with a solution, suspension, or emulsion of the polymer. Theresulting stabilized polymer compositions of the invention mayoptionally also contain from about 0.01 to about 5%, preferably fromabout 0.025 to about 2%, and especially from about 0.1 to about 1% byweight of various conventional additives, such as the materials listedbelow, or mixtures thereof.

[0117] 1. Antioxidants

[0118] 1.1. Alkylated Monophenols, for Example,

[0119] 2,6-di-tert-butyl-4-methylphenol

[0120] 2-tert-butyl-4,6-dimethylphenol

[0121] 2,6-di-tert-butyl-4-ethylphenol

[0122] 2,6-di-tert-butyl-4-n-butylphenol

[0123] 2,6-di-tert-butyl-4-1-butylphenol

[0124] 2,6-di-cyclopentyl-4-methylphenol

[0125] 2-(α-methylcyclohexyl)-4,6-dimethylphenol

[0126] 2,6-di-octadecyl-4-methylphenol

[0127] 2,4,6-tri-cyclohexylphenol

[0128] 2,6-di-tert-butyl-4-methoxymethylphenol

[0129] 1.2. Alkylated Hydroguinones, for Example,

[0130] 2,6-di-tert-butyl-4-methoxyphenol

[0131] 2,5-di-tert-butyl-hydroquinone

[0132] 2,5-1-tert-amyl-hydroquinone

[0133] 2,6-diphenyl-4-octadecyloxyphenol

[0134] 1.3. Hydroxylated Thiodiphenyl Ethers, for Example,

[0135] 2,2′-thio-bis-(6-tert-butyl-4-methylphenol)

[0136] 2,2′-thio-bis-(4-octylphenol)

[0137] 4,4′-thio-bis-(6-tert-butyl-3-methylphenol)

[0138] 4,4′-thio-bis-(6-tert-butyl-2-methylphenol)

[0139] 1.4. Alkylidene-Bisphenols, for Example,

[0140] 2,2′-methylene-bis-(6-tert-butyl-4-methylphenol)

[0141] 2,2′-methylene-bis-(6-tert-butyl-4-ethylphenol)

[0142] 2,2′-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

[0143] 2,2′-methylene-bis-(4-methyl-6-cyclohexylphenol)

[0144] 2,2′-methylene-bis-(6-nonyl-4-methylphenol)

[0145] 2,2′-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

[0146] 2,2′-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

[0147] 2,2′-methylene-bis-(4,6-di-tert-butylphenol)

[0148] 2,2′-ethylidene-bis-(4,6-di-tert-butylphenol)

[0149] 2,2′-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

[0150] 4,4′-methylene-bis-(2,6-di-tert-butylphenol)

[0151] 4,4′-methylene-bis-(6-tert-butyl-2-methylphenol)

[0152] 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

[0153] 2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

[0154] 1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

[0155]1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

[0156] ethyleneglycolbis-[3,3-bis-(3′-tert-butyl-4′-hydroxyphenyl)-butyrate]

[0157] di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

[0158]di-[2-(3′-tert-butyl-2′-hydroxy-5′-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

[0159] 1.5. Benzyl Compounds for Example,

[0160]1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

[0161] di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

[0162] 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctylester

[0163] bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiolterephthalate

[0164] 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate

[0165] 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate

[0166] 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecylester

[0167] 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethylester, calcium-salt

[0168] 1.6. Acylaminophenols, for Example,

[0169] 4-hydroxy-lauric acid anilide

[0170] 4-hydroxy-stearic acid anilide

[0171]2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

[0172] octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

[0173] 1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionicacid with monohydric or polyhydric alcohols, for example, methanoldiethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine triisopropanolamine

[0174] 1.8. Esters ofβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydricor polyhydric alcohols, for example, methanol diethylene glycoloctadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopentylglycol tris-hydroxyethyl isocyanurate thiodiethylene glycoldi-hydroxyethyl oxalic acid diamide triethanolamine triisopropanolamine

[0175] 1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionicacid for example,

[0176]N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

[0177]N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

[0178] N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

[0179] 1.10 Diarylamines, for example,

[0180] diphenylamine, N-phenyl-1-naphthylamine,N-(4-tert-octylphenyl)-1-naphthylamine,4,4′-di-tert-octyl-diphenylamine, reaction product ofN-phenylbenzylamine and 2,4,4-trimethylpentene, reaction product ofdiphenylamine and 2,4,4-trimethylpentene, reaction product ofN-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.

[0181] 2. UV Absorbers and Light Stabilizers

[0182] 2.1. 2-(2′-Hydroxyphenyl)-benzotriazoles, for example, the5′-methyl-, 3′,5′-di-tert-butyl-, 5′-tert-butyl-,5′-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3′,5′-di-tert-butyl-,5-chloro-3′-tert-butyl-5′-methyl-, 3′-sec-butyl-5′-tert-butyl-,4′-octoxy, 3′,5′-di-tert-amyl-, 3′,5′-bis-(α,α-dimethylbenzyl),3′-tert-butyl-5′-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3′-dodecyl-5′-methyl-, and 3′-tert-butyl-5′-(2-octyloxycarbonyl)ethyl-,and dodecylated-5′-methyl derivatives.

[0183] 2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-,4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy,4,2′,4′-trihydroxy- and 2′-hydroxy-4,4′-dimethoxy derivatives.

[0184] 2.3. Esters of optionally substituted benzoic acids for example,phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

[0185] 2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acidethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methylester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butylester, β-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

[0186] 2.5. Nickel compounds, for example, nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

[0187] 2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6 tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N′-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1′(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,1-(2-hydroxy-2-methylpropoxy)-4-octa-decanoyloxy-2,2,6,6-tetramethylpiperidine.

[0188] 2.7. Oxalic acid diamides, for example,4,4′-di-octyloxy-oxanilide, 2,2′-di-octyloxy-5,5′di-tert-butyl-oxanilide,2,2′-di-dodecyloxy-5,5′-di-tert-butyl-oxanilide,2-ethoxy-2′-ethyl-oxanilide, N,N′-bis (3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

[0189] 2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)-phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

[0190] 3. Metal deactivators, for example, N,N′-diphenyloxalic aciddiamide, N-salicylal-N′-salicyloyl-hydrazine,N,N′-bis-salicyloylhydrazine,N,N′-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

[0191] 4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecyl-pentaerythritol diphosphite,di-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4′-diphenylylenediphosphonite.

[0192] 5. Compounds which destroy peroxide, for example, esters ofα-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

[0193] 6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecyl-hydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

[0194] 7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecyInitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

[0195] 8. Polyamide stabilizers, for example copper salts in combinationwith iodides and/or phosphorus compounds and salts of divalentmanganese.

[0196] 9. Basic co-stabilizers, for example, melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal salts and alkaline earth metal salts of higher fatty acidsfor example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and Kpalmitate, antimony pyrocatecholate or zinc pyrocatecholate.

[0197] 10. Nucleating agents, for example, 4-tert-butyl-benzoic acid,adipic acid, diphenylacetic acid.

[0198] 11. Fillers and reinforcing agents, for example, calciumcarbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, bariumsulfate, metal oxides and hydroxides, carbon black, graphite.

[0199] 12. Other additives, for example, plasticizers, lubricants,emulsifiers, pigments, optical brighteners, flameproofing agents,anti-static agents, blowing agents and thiosynergists such as dilaurylthiodipropionate or distearyl thiodipropionate.

[0200] 13. Benzofuranones and indolinones, for example those disclosedin U.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No.5,175,312, or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)-benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-di-methyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

[0201] The co-stabilizers, with the exception of the benzofuranoneslisted under 13, are added for example in concentrations of 0.01 to 10%,relative to the total weight of the material to be stabilized.

[0202] Further preferred compositions comprise, in addition tocomponents (a) and (b) further additives, in particular phenolicantioxidants, light stabilizers or processing stabilizers.

[0203] Particularly preferred additives are phenolic antioxidants (item1 of the list), sterically hindered amines (item 2.6 of the list),phosphites and phosphonites (item 4 of the list), UV absorbers (item 2of the list) and peroxide-destroying compounds (item 5 of the list).

[0204] Additional additives (stabilizers) which are also particularlypreferred are benzofuran-2-ones, such as described, for example, in U.S.Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312.

[0205] The phenolic antioxidant of particular interest is selected fromthe group consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,2,2′-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-1-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N′-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

[0206] A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4 hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-tri-methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2′-ethylidene-bis(4,6-di-tert-butylphenol).

[0207] The hindered amine compound of particular interest is selectedfrom the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4′-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of2,4-dichloro-6-morpholino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N′″-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl] 1,2,3,4-butanetetracarboxylate, mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, octamethylenebis(2,2,6,6-tetramethyl-piperidin-4-carboxylate),4,4′-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethyl-piperidin-4-yl-n-dodecylsuccinimide,N-1,2,2,6,6-pentamethyl-piperidin-4-yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine,bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)]sebacate; a mixture ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarate andbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate;1-(2-hydroxy-2-methyl-propoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-piperidin-4-yl]glutarate;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]succinate; a mixture of bis1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarate andbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]succinate;1-(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-octadecanoyloxy-2-methylpropane;1-(2-hydroxy-2-methylpropoxy)-4-[9-(methoxy-carbonyl)nonanoyloxy]-2,2,6,6-tetramethyl-piperidine;1-(2-hydroxy-2-methylpropoxy)-4-[5-(methoxy-carbonyl)pentanoyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[3-(methoxy-carbonyl)propionyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[4-(methoxy-carbonyl)-butyryloxy]-2,2,6,6-tetramethylpiperidine;condensation product of4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidinewith hexamethylene diisocyanate and terminated with methoxy;condensation product of4-hydroxy-1-(2-hydroxy-ethoxy)-2,2,6,6-tetramethyl-piperidine withhexamethylene diisocyanate and terminated with methoxy; and thecondensation product of4-hydroxy-1-(2-hydroxy-1-phenethoxy)-2,2,6,6-tetramethylpiperidine withhexamethylene diisocyanate and terminated with methoxy.

[0208] A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N′″-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecanedi-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine,or1-(2-hydoxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine.

[0209] The instant composition can additionally contain another UVabsorber selected from the group consisting of the benzotriazoles, thes-triazines, the oxanilides, the salicylates, the hydroxybenzophenones,the benzoates and the α-cyanoacrylates.

[0210] Particularly, the instant composition may additionally contain aneffective stabilizing amount of at least one other2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; orhindered amine or mixtures thereof.

[0211] Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected fromthe group consisting of

[0212] 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

[0213] 2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;

[0214]2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;

[0215] 2-(2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl{-2H-benzotriazole;

[0216] 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

[0217]5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;

[0218] 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; and

[0219] 2-f2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H—benzotriazole.

[0220] Preferably, the other tris-aryl-s-triazine is selected from thegroup consisting of

[0221]2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

[0222] 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-phenyl]-s-triazine;

[0223]2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxy-propyloxy)-5-α-cumylphenyl]-s-triazine.(* denotes a mixture of octyloxy, nonyloxy and decyloxy groups.), and

[0224]2,4-bis(biphenylyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)phenyl]-s-triazine.(* denotes a mixture of octyloxy, nonyloxy and decyloxy groups.)

[0225] The instant compounds are often used in conjunction with one ormore coadditive stabilizers where the coadditive stabilizer is ahindered phenolic antioxidant selected from the group consisting ofneopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate,octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5,-di-tert-butyl-4-hydroxybenzyl)benzene,1,2-bis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamoyl)hydrazine, calcium[bis(monoethyl 3,5-ditert-butyl-4-hydroxybenzyl)-phosphonate],1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl) isocyanurate; oris an organophosphorus stabilizer selected from the group consisting oftris(2,4-di-tert-butylphenyl) phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,2,2′,2″-nitrilo[triethyl-tris-(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], tetrakis(2,4-di-butylphenyl) 4,4′-biphenylenediphosphonite,tris(nonylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythrityl diphosphite, 2,2′-ethylidenebis(2,4-di-tert-butylphenyl)fluorophosphite and 2-butyl-2-ethylpropan-1,3-diyl2,4,6-tri-tert-butylphenyl phosphite; or is5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-2H-benzofuran-2-one; or isN,N-dialkylhydroxyl-amine made by the direct oxidation ofN,N-di(hydrogenated tallow)amine; or is a hindered amine selected fromthe group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,the polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid,N,N′,N″,N′″-tetrakis[4,6-bis(butyl-1,2,2,6,6-penta-methylpiperidin-4-yl)amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,the polycondensation product of4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and2,4-dichloro-6-tert-octylamino-s-triazine, the polycondensation productof 4,4′-hexa-methylenebis(amino-2,2,6,6-tetramethylpiperidine) and2,4-dichloro-6-morpholino-s-triazine, the polycondensation product of4,4′-hexamethylenebis(amino-1,2,2,6,6-penta-methylpiperidine) and2,4-dichloro-6-morpholino-s-triazine, 2,2,6,6-tetramethylpiperidin-4-yloctadecanoate,3-dodecyl-1-(1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)-pyrrolidin-2,5-dione,1,3,5-tris(N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)ethyl]amino)-s-triazine,poly[methyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)-propyl]siloxane,the polycondensation product of2,4-dichloro-6-(2,2,6,6-tetramethyl-piperidin-4-yl)butylamino)-s-triazine,2,2′ethylene-bis([2,4-(2,2,6,6-tetramethyl-piperidin-4-yl)butylamino-s-triazin-6-yl]aminotrimethyleneamino),oligomer ofN-{[2-(N-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl, N,N′,N″-tris(2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl)-3,3′-ethylenediiminodipropylamine,N,N′,N″′-tris(2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl)-3,3′-ethylenediiminodipropylamineand N,N′,N″,N′″-tetrakis(2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl)-3,3′-ethylenediiminodipropylamine;or is another N-hydrocarbyloxy substituted hindered amines selected fromthe group consisting ofbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,bis(1-cyclo-hexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl octadecanoate,N,N′,N″-tris(2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-6-yl)-3,3′-ethylenediiminodipropylamine,N,N′,N′″-tris(2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-6-yl)-3,3′-ethylenediiminodipropylamineandN,N′,N″,N′″-tetrakis(2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-6-yl)-3,3′-ethylenediiminodipropylamine;or a hydroxy substituted N-hydrocarbyloxy substituted hindered amineselected from the group consisting ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)]sebacate; a mixture ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarate andbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate;1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarate;bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]succinate; a mixture ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarate andbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]succinate;1-(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-octadecanoyl-oxy-2-methylpropane;1-(2-hydroxy-2-methylpropoxy)-4-[9-(methoxy-carbonyl)-nonanoyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[5-(methoxy-arbonyl)pentanoyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[3-(methoxy-carbonyl)propionyloxy]-2,2,6,6-tetramethylpiperidine;1-(2-hydroxy-2-methylpropoxy)-4-[4-(methoxy-carbonyl)butyryloxy]-2,2,6,6-tetramethyl-piperidine;or is a UV absorber selected from the group consisting of2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,2,4-di-tert-butylphenyl 3,5-di-tert-butyl4-hydroxybenzoate,2-hydroxy-4-n-octyloxybenzophenone,2,4-bis(2,4-dimethyphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine,oligomer of N—(2-[(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl)-N,N′-bis(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl, the condensationproduct of 2-morpholino-4,6-dichloro-s-triazine withN,N′-bis(1,2,2,6,6-pentamethyl-piperidin-4-yl)-1,6-hexanediamine; ormixtures thereof.

[0226] Preferably the coadditive stabilizer is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate,tris(2,4-di-tert-butylphenyl) phosphite, N,N-dialkylhydroxyl-amine madeby the direct oxidation of N,N-di(hydrogenated tallow)amine,N,N′,N″,N″-tetrakis[4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,the polycondensation product of4,4′-hexamethylene-bis(amino-2,2,6,6-tetramethylpiperidine) and2,4-dichloro-6-tert-octylamino-s-triazine, the polycondensation productof 4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and2,4-dichloro-6-morpholino-s-triazine, the polycondensation product of4,4′-hexa-methylenebis(amino-1,2,2,6,6-pentamethylpiperidine) and2,4-dichloro-6-morpholino-s-triazine, oligomer ofN-{2-(N-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl, N,N′,N″-tris(2,4-bis[N-(1,2,2,6,6-pentamethyl-piperidin-4-yl)butylamino]-s-triazin-6-yl)-3,3′-ethylenediiminodipropylamine,N,N′,N″′-tris(2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-ylbutylamino]-s-triazin-6-yl)-3,3′-ethylenediiminodipropylamineandN,N′,N″,N′″-tetrakis(2,4-bis[N-(1,2,2,6,6-penta-methylpiperidin-4-yl)butylamino]-s-triazin-6-yl)-3,3′-ethylenediiminodipropylamine,oligomer ofN-(2-[(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl)—N,N′-bis(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl, or thecondensation product of 2-morpholino-4,6-dichloro-s-triazine withN,N′-bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,6-hexanediamine.

[0227] The alkyd resin lacquers which can be stabilized against theaction of light and moisture in accordance with the instant inventionare the conventional stoving lacquers which are used in particular forcoating automobiles (automobile finishing lacquers), for examplelacquers based on alkyd/melamine resins and alkyd/acrylic/melamineresins (see H. Wagner and H. F. Sarx, “Lackkunstharze” (1977), pages99-123). Other crosslinking agents include glycouril resins, blockedisocyanates or epoxy resins.

[0228] The lacquers stabilized in accordance with the invention aresuitable both for metal finish coatings and solid shade finishes,especially in the case of retouching finishes, as well as various coilcoating applications. The lacquers stabilized in accordance with theinvention are preferably applied in the conventional manner by twomethods, either by the single-coat method or by the two-coat method. Inthe latter method, the pigment-containing base coat is applied first andthen a covering coat of clear lacquer over it.

[0229] It is also to be noted that the compounds of the presentinvention are applicable for use in non-acid catalyzed therm oset resinssuch as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyesterresins, optionally modified with silicon, isocyanates or iso-cyanurates.The epoxy and epoxy-polyester resins are crosslinked with conventionalcross-linkers such as acids, acid anhydrides, amines and the like.Correspondingly, the epoxide may be utilized as the crosslinking agentfor various acrylic or polyester resin systems that have been modifiedby the presence of reactive groups on the backbone structure.

[0230] When used in two-coat finishes, the compounds of the instantinvention can be incorporated in the clear coat or both in the clearcoat and in the pigmented base coat.

[0231] When water-soluble, water miscible or water dispersible coatingare desired ammonium salts of acid groups present in the resin areformed. Powder coating composition can be prepared by reacting glycidylmethacrylate with selected alcohol components.

[0232] The instant benzotriazoles are made by conventional methods forpreparing such compounds. The usual procedure involves the diazotizationof a substituted o-nitroaniline followed by coupling the resultantdiazonium salt with a substituted phenol and reduction of the azobenzeneintermediate to the corresponding desired benzotriazole. The startingmaterials for these benzotriazoles are largely items of commerce or canbe prepared by normal methods of organic synthesis.

[0233] While the instant benzotriazoles with their enhanced durabilityare particularly suited for automotive coating applications, it iscontemplated that they will also be espeically useful in otherapplications where their enhanced durability is required such as insolar films and the like.

[0234] The instant invention also pertains to candle wax compositionswhich comprises

[0235] (a) white and unscented, white and scented, dyed and unscented,dyed and scented, dipped and unscented or dipped and scented candle wax,and

[0236] (b) an effective stabilizing amount of a benzotriazole of formulaI or II as described above alone or in combination with a hinderedamine.

[0237] An effective amount of benzotriazole alone or plus the hinderedamine in the candle wax is 0.01 to 10% by weight, preferably 0.1 to 2%by weight; and most preferably 0.1 to 0.5% by weight based on the wax.When a combination of benzotriazole and hindered amine are used, theweight ratio of benzotriazole to hindered amine is 10:1 to 1:10;preferably 4:1 to 1:4; most preferably 2:1 to 1:2 based on the candlewax.

[0238] It should be noted that candles contain a host of variouscomponents. The base materials may be made up of the following:

[0239] paraffin wax,

[0240] natural oils,

[0241] polyamide plus fatty acid/ester,

[0242] fatty acids such as stearin,

[0243] opacifiers,

[0244] beeswax,

[0245] glycerides plus oxidized wax,

[0246] alcohols, and

[0247] ethylene oligomers.

[0248] Candles also contain a number of additives such as the following:

[0249] mold release agents,

[0250] fragrances,

[0251] insect repellants or insecticides,

[0252] hardeners,

[0253] crystal modifiers,

[0254] clarifiers,

[0255] guttering reducers,

[0256] colorants,

[0257] f.p. control agents,

[0258] stretchability improvers,

[0259] gelling agents,

[0260] extrusion aids, and

[0261] vortex reducers.

[0262] Each of the various components are meant to control or modify theproperties of the candle to insure proper burning, reduce channelling,aid in uniform melting, and the like. The colorants and fragrancesobviously are there to provide the proper color, scent or otheraesthetic appeal.

[0263] Of increasing importance are the transparent gel candles whichlook like clear glass, but which burn like a classical candle. As isdiscussed in detail in U.S. Pat. No. 5,879,694, the relevant parts ofwhich are incorporated herein by reference, these gel candles usuallycontain a copolymer selected from the group consisting of a triblock,radial block, diblock or multiblock copolymer classically made up of atleast two thermodynamically incompatible segments containing both hardand soft segments. Typical of such block copolymers is KRATON® (ShellChemical Co.) which consists of block segments of styrene monomer unitsand rubber monomer or comonomer units. The most common structure foundin KRATON® D series is a linear ABA block with styrene-butadiene-styrene(SBS) or styrene-isoprene-styrene (SIS).

[0264] Candles may also contain other stabilizers such as phenolicantioxidants, phosphites, hydroxylamines and the like, particularlyphenolic antioxidants such as are described above.

[0265] The following examples are for illustrative purposes only and arenot to be construed to limit the scope of the instant invention in anymanner whatsoever.

EXAMPLE 15-Phenyl-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole

[0266] (A) 3-Nitro-4-acetamido-1,1′-biphenyl

[0267] To a mixture of 4-acetamido-1,1′biphenyl (21.1 g, 0.1 mol) and150 mL of acetic anhydride maintained between 8° C. and 13° C. is slowlyadded dropwise over 32 minutes 12.7 mL of 70% nitric acid. The reactionmixture is added to 600 mL of a mixture of water and ice and theresultant precipitate is collected by filtration. The filter cake iswashed with water and the residue is recrystallized from methanol (800mL) to give 23.6 g of the title compound as a yellow crystalline solidmelting at 129-132° C.

[0268] (B) 3-Nitro-4-amino-1,1′-biphenyl

[0269] A mixture of potassium hydroxide (2.5 g),3-nitro-4-acetamido-1,1′-biphenyl (23.5 g), prepared in (A) above, water(6 mL) and ethanol (12 mL) is heated at reflux for one hour. Thereaction mixture is cooled to room temperature and then poured into 300mL of a mixture of water and ice. The solid is collected by filtrationand the crude product is recrystallized from methanol (800 mL) to give14.1 g of the title compound as an orange solid melting at 170-172° C.

[0270] (C) 4-Phenyl-2-nitrobenzenediazonium Hydrogen Sulfate

[0271] To 70 mL of sulfuric acid at 10° C. is added portionwise sodiumnitrite (7 g, 0.1 mol). The reaction mixture is warmed to 20° C. todissolve all the sodium nitrite and then cooled to 15° C. To thereaction mixture is added over 30 minutes a suspension of3-nitro-4-amino-1,1′-biphenyl (7.33 g, 0.034 mol), prepared in (B)above, in 60 mL of acetic acid. The reaction mixture is stirred for onehour at 10° C. and then to the reaction mixture is added 500 mL ofdiethyl ether. An exotherm occurs. The mixture is stirred for one hour.The solid formed is removed by filtration behind a safety shield andwashed with diethyl ether to give 16.2 g of the title compound as ayellow solid. The solidis dried for 1.5 hours at 20° C. under vacuum andstored in a freezer in a polyethylene container until later use.Analysis: IR (nujol) v 1650 (N═N), 2250 (N₂ ⁺) cm⁻¹.

[0272] (D) 2-Hydroxy-2′nitro-3,4′-diphenyl-5-tert-octylazobenzene

[0273] To a solution of sodium hydroxide (12 g, 0.3 mol) and2-phenyl-4-tert-octylphenol (14.1 g, 0.05 mol) in 150 mL of methanolmaintained at 0-5° C. is added portionwise over 1.25 hours4-phenyl-2-nitrobenzenediazonium hydrogen sulfate (30.6 g, 0.065 mol),prepared in (C) above. The reaction mixture is stirred for two hours at0-5° C. Xylene (200 mL) is added to the reaction mixture. The organicphase is separated and extracted with water (4×200 mL). The organicphase is filtered and the solvent removed by distillation under anatmosphere of nitrogen. The residue is purified by flash chromatography(90:10 heptane:ethyl acetate eluent) to give 6.56 g of the titlecompound as a viscous dark red liquid.

[0274] (E)5-Phenyl-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole

[0275] To a solution of sodium hydroxide (6 g, 0.15 mol) in 8 mL ofwater is added 2-hydroxy-2′nitro-3,4′-diphenyl-5-tert-octylazobenzene(6.56 g), prepared in (D) above. The reaction mixture is heated toreflux and then formadine sulfinic acid (10.8 g, 0.1 mol) is addedportionwise over 20 minutes. The reaction mixture is heated at refluxfor 1.5 hours. To the cooled reaction mixture is added 200 mL of waterand the ethanol is removed under vacuum. The reaction mixture isadjusted to pH 4 with hydrochloric acid. The resultant mixture isextracted twice with methylene chloride and the combined organic phasesare extracted with water. The organic phase is dried ovdr anhydrousmagnesium sulfate, and the solvent is then removed under vacuum. Theresidue is recrystallized sequentially from a mixture of water andmethanol, and petroleum ether to give the title compound as a whitesolid melting at 123-125° C.

EXAMPLE 25-(4-Trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0276] This example illustrates the use of n-propanol as solvent andtriphenylphosphine as a ligand in the Suzuki reaction to make theinstant compound.

[0277] A flask, equipped with a mechanical stirrer and an inertatmosphere with a FIRESTONE® valve, containing a mixture of5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(5.21 g, 0.01 mol), 4-trifluoromethylphenylboronic acid (1.99 g, 0.0105mol) and 250 mL of n-propanol is evacuated and filled three times withnitrogen. To this mixture is then added palladium (II) diacetate (0.090g, 0.0004 mol), triphenylphosphine (0.315 g, 0.0012 mol), 6 mL of 2Msodium carbonate (1.27 g, 0.012 mol) and 10 mL of water. The flask isthen evacuated and filled with nitrogen three times. The reactionmixture is stirred for 15 minutes at room temperature and then heated to85° C. The reaction mixture is heated at 85° C. for four hours and thenallowed to cool to room temperature. The solvent is removed under vacuumand the residue is partitioned between diethyl ether (250 mL) and water(100 mL). The organic phase is separated and extracted sequentially with5% aqueous sodium bicarbonate (100 mL) and saturated aqueous sodiumchloride (100 mL). The organic phase is dried over anhydrous sodiumsulfate and the volatiles are removed under vacuum. The residue isrecrystallized from isopropanol (250 mL) to give 3.59 g (61% yield) of alight yellow solid. An analytical sample is prepared by dissolving theproduct in toluene (25 mL) and treating the resultant solution withactivated carbon followed by chromatography (silical gel; ethyl acetateeluent) to give 2.87 g of the tide compound as a pale yellow solid.Further purification is effected by sublimation to give a productmelting at 146-147.5° C. IHnmr (CDCl₃; 499.8494 MHz) δ 0.84 (s, 9H);1.52 (s, 6H); 1.83 (s, 6H); 1.86 (s, 2H); 7.15-7.30 (overlappingmultiplets, 5H); 7.65 (d, 1H); 7.69 (d, 1H); 7.77 (multiplet, 4H); 7.96(d, 1H); 8.05 (d, 1H); 8.36 (d, 1H); 11.33 (s, 1H);

[0278]¹⁹Fnmr (CDCl₃; 282.3300 MHz) 6-69.04;

[0279] Analysis:

[0280] Calcd for C₃₆H₃₈F₃N₃O: C, 73.82; H, 6.54; N, 7.17. Found: C,73.82; H, 6,46; N, 7.07.

EXAMPLE 35-(4-Trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0281] This example illustrates the use of isopropanol as solvent andtriphenylphosphine as a ligand in the Suzuki reaction to make theinstant compound.

[0282] The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(1.04 g, 0.002 mol), 4-trifluoromethylphenylboronic acid (0.40 g, 0.0021mol), palladium (II) diacetate (0.045 g, 0.0002 mol), triphenylphosphine(0.160 g, 0.0006 mol), 1.2 mL of 2M sodium carbonate (0.25 g, 0.0024mol), 2 mL of water and 50 mL of isopropanol at 79° C. for five hours togive 0.97 g (83% yield) of the title compound as a solid identical tothat prepared in Example 2.

EXAMPLE 45-(4-Trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0283] This example illustrates the use of dioxane as solvent,2-(di-tert-butylphosphino)-biphenyl as a ligand, and potassium fluoridein place of sodium carbonate in the Suzuki reaction to make the instantcompound.

[0284] The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(1.04 g, 0.002 mol), 4-trifluoromethylphenylboronic acid (0.57 g, 0.003mol), palladium (II) diacetate (0.045 g, 0.0002 mol),2-(di-tert-butyl-phosphino)biphenyl (0.119 g, 0.0004 mol), potassiumfluoride (0.34 g, 0.0006 mol) and 30 mL of dioxane at 67° C. for 1.25hours to give 0.46 g (39% yield) of the title compound as a solididentical to that prepared in Example 2.

EXAMPLE 5 5-(4-Trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0285] This example illustrates the use of dioxane as solvent,1,1′-bis[2,4,8,10-tetrakis-(tert-butyl)-dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]ferroceneas a ligand, and potassium fluoride in place of sodium carbonate in theSuzuki reaction to make the instant compound.

[0286] The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(1.04 g, 0.002 mol), 4-trifluoromethylphenylboronic acid (0.57 g, 0.003mol), palladium (II) diacetate (0.045 g, 0.0002 mol),1,1′-bis[2,4,8,10-tetrakis(tert-butyl)-dibenzo[d,f[]1,3,2]dioxaphosphepin-6-yl]ferrocene(0.425 g, 0.0004 mol), potassium fluoride (0.34 g, 0.0006 mol) and 30 mLof dioxane at 67° C. for 1.25 hours to give 0.84 g (72% yield; drycolumn chromatography; 9:1 heptane:ethyl acetate eluent) of the titlecompound as a solid identical to that prepared in Example 2.

EXAMPLE 65-(3-Trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0287] This example illustrates the use of isopropanol as solvent andtriphenylphosphine as a ligand in the Suzuld reaction to make theinstant compound.

[0288] The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(1.04 g, 0.002 mol), 3-trifluoromethylphenylboronic acid (0.40 g, 0.0021mol), palladium (II) diacetate (0.045 g, 0.0002 mol), triphenylphosphine(0.160 g, 0.0006 mol), 1.2 mL of 2M sodium carbonate (0.25 g, 0.0024mol), 2 mL of water and 50 mL of isopropanol at 79° C. for five hours.The residue is purified by recrystallization from isopropanol (20 mL)followed by chromatography (acid alumina; 9:1 heptane:ethyl acetateeluent) to give 0.80 g (68% yield) of the title compound as a lightyellow solid melting at 138-139.5° C.

[0289]¹Hnmr (CDCl₃; 499.8494 MNFz) δ 0.81 (s, 9H); 1.52 (s, 6H); 1.83(s, 6H); 1.86 (s, 2H); 7.15-7.32 (overlapping multiplets, 5H); 7.62 (dd,1H); 7.64 (d, 1H); 7.67 (d, 1H); 7.69 (dd, 1H); 7.84 (d, 1H); 7.91(unresolved d, 1H); 7.95 (d, 1H); 8.05 (d, 1H); 8.36 (d, 1H); 11.33 (s,1H);

[0290]¹⁹Fnmr (CDCl₃; 282.3300 MHz) δ −69.04;

[0291] MS (DIP) m/z 585 (M+)

[0292] Analysis:

[0293] Calcd for C₃₆H₃₈F₃N₃O: C, 73.82; H, 6.54; N, 7.17. Found: C,73.48; H, 6,46; N, 6.92.

EXAMPLE 75-(3-Trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0294] This example illustrates the use of n-propanol as solvent andtriphenylphosphine as a ligand in the Suzuki reaction to make theinstant compound.

[0295] The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(5.21 g, 0.01 mol), 3-trifluoromethylphenylboronic acid (1.99 g, 0.0105mol), palladium (II) diacetate (0.090 g, 0.0004 mol), triphenylphosphine(0.315 g, 0.0012 mol), 6 mL of 2M sodium carbonate (1.27 g, 0.012 mol),10 mL of water and 250 mL of n-propanol at 84° C. for 3.5 hours to give5.17 g (88% yield) of the title compound as a solid identical to thecompound prepared in Example 6.

EXAMPLE 85-(2-Trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0296] This example illustrates the use of isopropanol as solvent andtriphenylphosphine as a ligand in the Suzuki reaction to make theinstant compound.

[0297] The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(2.60 g, 0.005 mol), 2-tiifluoromethylphenylboronic acid (0.997 g,0.00525 mol), palladium (II) diacetate (0.045 g, 0.0002 mol),triphenylphosphine (0.157 g, 0.0006 mol), 3 mL of 2M sodium carbonate(0.64 g, 0.006 mol), 5 mL of water and 200 mL of n-propanol at 91° C.for two hours. The residue is purified by chromatography (tolueneeluent) followed by recrystallization from isopropanol (50 mL) to give1.85 g (63% yield) of the title compound as a yellow solid melting at133.5-136° C.

[0298]¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.84 (s, 9H); 1.52 (s, 6H); 1.83 (s,6H); 1.86 (s, 2H); 7.15-7.32 (overlapping multiplets, 5H); 7.40(overlapping d, 2H); 7.53 (dd, 1H); 7.61 (dd, 1H); 7.64 (d, 1H); 7.80(multiplet, 2H); 7.88 (d, 1H); 8.36 (d, 1H); 11.35 (s, 1H);

[0299]¹⁹Fnmr (CDCl₃; 282.3300 MHz) δ −63.4;

[0300] MS (DIP) m/z 585 (M⁺)

EXAMPLE 95-Phenyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0301] (A) 2-Hydroxy-2′nitro-3-α-cumyl-4′-phenyl-5-tert-octylazobenzene

[0302] The procedure of Example 1 (D) is followed using sodium hydroxide(4 g, 0.1 mol), methanol (100 mL), 4-phenyl-2-nitrobenzenediazoniumhydrogen sulfate (16 g, 0.034 mol) and 2-α-cumyl-4-tert-octylphenol (8.1g, 0.028 mol) to give the title compound as a dark red solid melting at176-179° C.

[0303] (B)5-Phenyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0304] The procedure of Example 1 (E) is followed using sodium hydroxide(4 g, 0.1 mol), 5 mL of water,2-hydroxy-2′nitro-3-α-cumyl-4′-phenyl-5-tert-octylazobenzene (4 g,0.0072 mol) and fomamidine sulfinic acid (6.5 g, 0.06 mol) to give thetitle compound as a pale yellow crystalline solid melting at 137-139° C.

[0305]¹Hnmr (CDCl₃) δ 0.84 (s, 9H); 1.52 (s, 6H); 1.83 (s, 6H); 1.86 (s,2H); 7.15-7.32 (overlapping multiplets, 5H); 7.41 (t, 1H); 7.50 (dd,2H); 7.63 (d, 1H); 7.67 (d, 2H); 7.71 (dd, 1H); 7.92 (d, 1H); 8.01 (d,1H); 8.35 9D, 1h); 11.41 (s, 1H).

[0306] Analysis:

[0307] Calcd for C₃₅H₃₉N₃O: C, 81.20; H, 7.59; N, 8.12. Found: C, 80.97;H, 7.54; N, 8.07.

EXAMPLE 105-Phenyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0308] The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(5.21 g, 0.01 mol), phenylboronic acid (1.28 g, 0.0105 mol), palladium(II) diacetate (0.090 g, 0.0004 mol), triphenylphosphine (0.315 g,0.0012 mol), 6 mL of 2M sodium carbonate (1.27 g, 0.012 mol), 10 mL ofwater and 250 mL of isopropanol at 84° C. for 3.5 hours. The titlecompound is obtained as a solid which is identical to that prepared inExample 9.

EXAMPLE 115-(3,5-Di-trifluoromethylphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0309] The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole1.04 g, 0.002 mol), 3,5-di-trifluoromethylphenyl-boronic acid (0.54 g,0.0021 mol), palladium (II) diacetate (0.045 g, 0.0002 mol),triphenylphosphine (0.160 g, 0.0006 mol), 1.2 mL of 2M sodium carbonate(0.25 g, 0.0024 mol), 2 mL of water and 50 mL of isopropanol at 79° C.for five hours. The residue is purified by recrystallizationsequentially from isopropanol (20 mL) and acetonitrile (10 mL) to give0.44 g (34% yield) of the title compound as a light yellow solid meltingat 79-81° C.

[0310]¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.84 (s, 9H); 1.52 (s, 6H); 1.83 (s,6H); 1.86 (s, 2H); 7.167.32 (overlapping multiplets, 5H); 7.66 (d, 1H);7.69 (dd, 1H); 7.92 (d, 1H); 8.00 (d, 1H); 8.09 (d, 2H); 8.10 (d, 1H);8.36 (d, 1H); 11.25 (s, 1H);

[0311]¹⁹Fnmr (CDCl₃; 282.3300 MHz) δ −69.4;

[0312] Analysis:

[0313] Calcd for C₃₇H₃₇F₆N₃O: C, 67.98; H, 5.71; N, 6.43. Found: C,67.66; H, 5.66; N, 6.34.

EXAMPLE 125-(1,1′-Biphenyl-4-yl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0314] The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole1.04 g, 0.002 mol), (1,1′-biphenyl-4-yl)boronic acid (0.42 g, 0.0021mol), palladium (II) diacetate (0.045 g, 0.0002 mol), triphenylphosphine(0.160 g, 0.0006 mol), 1.2 mL of 2M sodium carbonate (0.25 g, 0.0024mol), 2 mL of water and 50 mL of isopropanol at 79° C. for five hours.The residue is purified by recrystallization sequentially from a mixtureof toluene (10 mL) and ethyl acetate (100 mL), and heptane (10 mL) togive 0.46 g (39% yield) of the title compound as an off-white solidmelting at 181-183° C.

[0315]¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.84 (s, 9H); 1.53 (s, 6H); 1.83 (s,6H); 1.86 (s, 2H); 7.13-7.32 (overlapping multiplets, 5H); 7.39 (t, 1H);7.49 (dd, 2H); 7.63 (d, 1H); 7.67 (d, 2H); 7.75 (m, 4H); 7.76 (dd, 1H);7.93 (d, 1H); 8.07 (d, 1H); 8.36 (d, 1H); 11.40 (s, 1H);

[0316] Analysis:

[0317] Calcd for C₄₁H₄₃F₃N₃O: C, 82.93; H, 7.30; N, 7.08. Found: C,83.12; H, 7.23; N, 6.88.

EXAMPLE 135-(4-Cyanophenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0318] The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole1.04 g, 0.002 mol), 4-cyanophenylboronic acid (0.42 g, 0.0021 mol),palladium (11) diacetate (0.045 g, 0.0002 mol), triphenylphosphine(0.160 g, 0.0006 mol), 1.2 mL of 2M sodium carbonate (0.25 g, 0.0024mol), 2 mL of water and 50 mL of isopropanol at 79° C. for five hours.The residue is purified by recrystallization from heptane followed bydry-column chromatography (9:1 heptane:ethyl acetate eluent) to give0.18 g (17% yield) of the title compound as a light yellow crystallinesolid melting at 163-164.5° C.

[0319]¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.84 (s, 9H); 1.52 (s, 6H); 1.83 (s,6H); 1.86 (s, 2H); 7.15-7.32 (overlapping multiplets, 5H); 7.65 (d, 1H);7.67 (dd, 1H); 7.76 (d, 2H); 7.79 (d, 2H); 7.97 (d, 1H); 8.05 (d, 1H);8.35 (d, 1H); 11.30 (s, 1H);

[0320] MS (DIP) m/z 542 (M+)

[0321] Analysis:

[0322] Calcd for C₃₆H₃₈N₄O: C, 79.67; H, 7.06; N, 10.32. Found: C,79.79; H, 7.12; N, 10.19.

EXAMPLE 145-Bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benwtriazole

[0323] This compound is an important intermediate for the preparation ofthe instant compounds by the Suzuki reaction by reaction with variousarylboronic acids or esters.

[0324] (A) 2-Hydroxy-2′nitro-3-α-cumyl-4′-bromo-5-tert-octylazobenzene

[0325] Diazotization and coupling: 96% Sulfuric acid (243 g) is chargedto a 2L jacketed reactor and the internal temperature is adjusted to 20°C. 40% (wt/wt) nitrosylsulfuric acid (335.4 g in sulfuric acid, 1.06mol) is added via an addition funnel keeping the internal temperaturebelow 20° C. At the end of this dilution step, the solution is cooled to0° C. and 217 g of 92.1% pure 4-bromo-2-nitroaniline (0.921 mol) isadded in portions keeping the internal temperature between 15-20° C. Thereaction mixture is stirred at room temperature for five hours. Water(674 g) is added over a two-hour period while keeping the internaltempearature at 0-5° C. The solution is filtered through a coarse funneland stored at 0° C. Titration of the diazo solution shows an sulfuricacid assay of 31.8% and a diazo assay of 17.9% (a yield of 86.2% ofdiazo compound based on the 4-bromo-2-nitroaniline).

[0326] In a 1L jacketed reactor is added 94.9 g of 96% pure2-α-cumyl-4-tert-octylphenol (0.281 mol) and 249.5 g of xylene followedby 4.1 g of HOSTAPUR® SAS 93. The mixture is dissolved at 28° C. and thetemperature held there. The diazonium salt solution prepared above (723g, 0.397 mol) is added to this solution over a period of six hours. Atthe end of the addition period, the transfer line is rinsed with 10.8 gof water and the reaction mixture is stirred for another 30 minutes. Thereaction temperature is raised to 60° C. and stirring stopped. Themixture divided into two phases which are separated. 370.3 g of a xylenesolution of2-hydroxy-2′-nitro-3-α-cumyl-4′-phenyl-5-tert-octylazobenzene isobtained. The xylene is removed under vacuum and methanol is added tocrystallize the product.

[0327]¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.83 (s, 9H); 1.44 (s, 6H); 1.78 (s,2H); 1.79 (s, 6H); 7.13-7.28 (overlapping multiplets, 5H); 7.62 (d, 1H);7.68 (d, 1H); 7.79 (dd, 1H); 7.85 (d, 1H); 8.19 (d, 1H); 12.94 (s, 1H).

[0328] (B)5-Bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole

[0329] To 2-butanol (200 mL) and sodium hydroxide (4.8 g, 0.1203 mol) at94° C. in a 2L Swiss reaction is added dropwise a solution of2-hydroxy-2′nitro-3-α-cumyl-4′-phenyl-5-tert-octylazobenzene (24.4 g,0.043 mol) and 2,3-dichloro-1,4-naphthoquinone (1.14 g, 0.005 mol) inmethyl ethyl ketone (60 mL) over a period of 1.5 hours while maintainingthe temperature of the reaction mixture over 90° C. Water and methylethyl ketone distill off during this period. After the reaction mixtureis held for one hour at about 90° C., the reduction is complete as seenby a sample tested by HPLC. The reaction mixture is cooled to 30° C. and31 mL of 30% sulfuric acid is added all at once. After further coolingto 5° C., the product precipitates along with a mixture of salts. Theprecipitate is isolated by filtration and freed of salts by repeatedwashing with water. Organic impurities are removed by washing with 200mL of cold methanol. The title compound is obtained after drying in ayield of 73% (16.4 g) as a light beige solid melting at 113-117° C.

[0330]¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.83 (s, 9H); 1.51 (s, 6H); 1.81 (s,6H); 1.85 (s, 2H); 7.15-7.30 (overlapping multiplets, 5H); 7.51 (dd,1H); 7.64 (d, 1H); 7.75 (d, 1H); 8.04 (d, 1H); 8.31 (d, 1H); 11.15 (s,1H).

EXAMPLE 155-(4-Methoxyphenyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0331] The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole1.56 g, 0.0105 mol), 4-methoxyphenylboronic acid (1.56 g, 0.0105 mol),palladium (II) diacetate (0.090 g, 0.0004 mol), triphenylphosphine(0.315 g, 0.0012 mol), 6 mL of 2M sodium carbonate (1.27 g, 0.0012 mol),10 mL of water and 250 mL of isopropanol at 90.5° C. for one hour. Theresidue is purified by dry-column flash chromatography (toluene eluent)and recrystallization from heptane (2×) to give 2.00 g (36.5% yield) ofthe title compound as light yellow crystals melting at 129-131° C.

[0332]¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.84 (s, 9H); 1.52 (s, 6H); 1.83 (s,6H); 1.86 (s, 2H); 3.89 (s, 3H); 7.03 (d, 2H); 7.14-7.32 (overlappingmultiplets, 5H); 7.61 (d, 2H); 7.62 (d, 1H); 7.68 (dd, 1H); 7.89 (dd,1H); 7.95 (multiplet, 1H); 8.34 (d, 1H); 11.41 (s, 1H);

[0333] Analysis:

[0334] Calcd for C₃₆H₄₁N₃O₂: C, 78.94; H, 7.54; N, 7.67. Found: C,79.11; H, 7.43; N, 7.59.

EXAMPLE 161,4-Bis[2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazol-5-yl]benzene

[0335] The procedure of Example 2 is followed using5-bromo-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole(5.73 g, 0.011 mol), 1,4-phenylenebis(boronic acid) (0.83 g, 0.005 mol),palladium (II) diacetate (0.090 g, 0.0004 mol), triphenylphosphine(0.315 g, 0.0012 mol), 6 mL of 2M sodium carbonate (1.27 g, 0.012 mol),10 mL of water and 250 mL of isopropanol at 88° C. for three hours. Theresidue is purified by dry-column flash chromatography (toluene eluent)and recrystallization from heptane to give 2.58 g (53.9% yield) of thetitle compound as light yellow crystals melting at 247-249° C.

[0336] (Dry-column flash chromatography is described by J. Leonard, B.Lygo and G. Proctor, in “Advanced Practical Organic Chemistry”, 2ndEdition, Blackie Academic & Professional, London, 1965, pp 215-216.)

[0337]¹Hnmr (CDCl₃; 499.8494 MHz) δ 0.84 (s, 18H); 1.53 (s, 12H); 1.84(s, 12H); 1.87 (s, 4H); 7.15-7.34 (overlapping multiplets, 10H); 7.64(d, 2H); 7.77 (dd, 2H); 7.80 (s, 4H); 7.95 (d, 2H); 8.09 (d, 2H); 8.36(d, 2H); 11.40 (s, 2H).

[0338] Analysis:

[0339] Calcd for C₆₄H₇₂N₆O₂: C, 80.30; H, 7.58; N, 8.78. Found: C,80.20; H, 7.63; N, 8.59.

EXAMPLE 175-(4-Methoxyphenyl)-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole

[0340] The procedure of Example 2 is followed using5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole3.58 g, 0.01 mol), 4-methoxyphenylboronic acid (3.04 g, 0.002 ml),palladium (II) diacetate (0.224 g, 0.001 mol),2-(dicyclohexyl-phosphino)biphenyl (0.701 g, 0.002 mol), potassiumfluoride (1.16 g, 0.02 mol) and 200 mL of dioxane at 88° C. for twohours. The residue is purified by dry-column flash chromatography(silica gel, 93:5 heptane:ethyl acetate eluent) followed by dissolvingin 50 mL of toluene and extraction with 5% aqueous sodium bicarbonate(20 mL) and saturated sodium chloride solution (20 mL). The toluenesolution is dried over anhydrous sodium sulfate and the solvent removedunder vacuum to give 0.60 g (14% yield) of the title compound as lightyellow solid.

[0341]¹Hnmr (CDCl₃; 499.8494 MHz) δ 1.42 (s, 9H); 1.53 (s, 9H); 3.90 (s,3H); 7.05 (d, 2H); 7.44 (d, 1H); 7.64 (d, 2H); 7.73 (dd, 1H); 7.98 (d,1H); 8.04 (d, 1H); 8.31 (d, 1H); 11.79 (s, 1H).

[0342] MS (DIP) 429 (M⁺).

EXAMPLE 185-(4-Trifluoromethylphenyl)-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole

[0343] The procedure of Example 2 is followed using5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)-2H-benzotriazole3.58 g, 0.01 mol), 4-trifluoromethylphenylboronic acid (2.85 g, 0.015ml), palladium (II) diacetate (0.224 g, 0.001 mol),2-(di-tert-butyl-phosphino)biphenyl (0.596 g, 0.002 mol), potassiumfluoride (1.16 g, 0.02 mol) and 200 mL of dioxane at 88° C. for twohours. The residue is purified by dry-column flash chromatography(silica gel, 93:5 heptane:ethyl acetate eluent) to give 0.64 g (13.7%yield) of the title compound as light yellow solid.

[0344] MS (DIP) 467 (M+).

[0345] Analysis:

[0346] Calcd for C₃₆H₄₁N₃O₂: C, 78.94; H, 7.54; N, 7.67. Found: C,79.11; H, 7.43; N, 7.59.

EXAMPLE 19 Polycarbonate

[0347] The durability of representative instant benzotriazoles inthermoplastic substrates is determined by incorporating various testcompounds into solvent cast films of polycarbonate resins. The freestanding films are mounted into cardboard holders, secured in metalframes and exposed in an Atlas C165 Xenon-arc Weather-Ometer under dryconditions according to ASTM G26. Loss of UV absorber is determined bymonitoring the loss of diagnostic UV absorption.

[0348] Polycarbonate flake (LEXAN® 145, General Electric) is dissolvedin methylene chloride at room temperature along with between 1 and 3% byweight of test benzotriazole, based on the polycarbonate. Films are castusing a calibrated drawdown bar to prepare 1 mil thick film afterdrying.

[0349] The instant compounds are particularly efficacious when used inthermoplastic compositions, such as polycarbonate. This is shown by thereduction in absorbance loss after exposure to actinic radiation.

EXAMPLE 20 Polycarbonate

[0350] Polycarbonate films of about 1 mil thickness and containing a UVabsorber are prepared by dissolving polycarbonate granules (LEXAN® 145,General Electric) and UV absorbers in methylene chloride and casting thefilms on a glass plate using a drawdown bar. The films are exposed for750 hours in a Xenon Arc Weather-Ometer according to ASTM G26 testmethod and the color change (ΔYI) versus that for unexposed films arerecorded below. The color measurements (yellowness index —YI) arecarried out on an ACS spectrophotometer, small area view, spectralcomponent included d/8, D65, 10° observer, YI 1925 for unexposed andexposed samples after 750 hours.

[0351] The instant compounds are particularly efficacious when used inthermoplastic compositions, such as polycarbonate. This is shown by thereduction of yellowing (ΔYI) after exposure to actinic radiation.

EXAMPLE 21 Poly(Methyl Methacrylate)

[0352] The durability of representative instant benzotriazoles inthermoplastic substrates is determined by incorporating various testcompounds into solvent cast films of a poly(methyl methacrylate) (PMMA)resin. The free standing films are mounted into cardboard holders,secured in metal frames and exposed in an Atlas C165 Xenon-arcWeather-Ometer under dry conditions according to ASTM G26. Loss of UVabsorber is determined by monitoring the loss of diagnostic UVabsorption as described earlier. Performance is measured by a change incolor or the physical integrity of the film, or in loss of absorbance ofthe UV absorber at % max.

[0353] Poly(methyl methacrylate), medium molecular weight, Aldrich, isdissolved in methylene chloride at room temperature along with between 1and 3% by weight of test benzotriazole, based on the PMMA resin. Filmsare cast using a calibrated drawdown bar to prepare 1 mil thick filmafter drying.

[0354] The instant compounds are particularly efficacious when used inthermoplastic compositions, such as poly(methyl methacrylate). This isshown by the reduction in absorbance loss after exposure to actinicradiation.

EXAMPLE 22 Incorporation into Photographic Layers

[0355] A gelatin coat of the following composition (per m²) is appliedin the customary manner to a polyester base. Components Amount Gelatin1200 mg Tricresyl Phosphate  510 mg Hardener*  40 mg Wetting Agent** 100 mg Test UV Absorber  400 mg

[0356] The gelatin coats are dried at 20° C. for seven days.

[0357] When the instant UV absorbers are used, clear transparent coatsare obtained which are suitable for photographic recording material forexample as a UV filter coat. This is seen by measuring the % Change inInitial Optical Density (2.0) after UV exposure. The instant compoundswhen used in a photographic layer are extremely photostable.

EXAMPLE 23 Automotive Coating Compositions

[0358] To ascertain the effect on thermal durability and loss rate froma high solids thermoset acrylic coating containing an instantbenzotriazole UV absorber, the following tests are carried out.

[0359] A high solids thermoset acrylic clear coat is prepared by mixingan experimental acrylic polyol resin and hexamethoxymethylmelamine(Resimene® 747, Monsanto) at a solids ratio of 60/40. The dodecylbenzenesulfonic acid catalyst (Nacure® 5225; King Industries) is added at 0.70%by weight. A flow aid Modaflow® (Monsanto) is added at 0.25% by weightto form a model acrylic melamine resin system.

[0360] The model clear coat is reduced with xylene to a viscosity of2627 second using a Zahn #2 cup and applied via a conventional air sprayat 50 psi (3.5 Kg/cm²) over a 1″×3″ (2.54 cm×7.62 cm) quartz slide. Cureis achieved by baking the slide for 30 minutes at 260° F. (127° C.). Theclear coat is stabilized with 1% by weight of a hindered amine lightstabilizer, bis-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,(TINUVIN® 123, Ciba). The various test benzotriazole UV absorbers areincorporated at the 5 mmol % by weight in the clear coat. The filmthickness on the quartz slides range from 1.15 to 1.41 mils (0.029 to0.036 mm).

[0361] The films on the quartz slides are weathered according to thefollowing conditions in Xenon Arc Weather-Ometer with a controlledirradiance at 6500 W, using inner quartz and outer borosilicate S-typefilter. The irradiation cycle is as follows: 40 minutes of straightirradiation with no water spray, followed by 20 minutes of light plusfront spray, followed by 60 minutes of light irradiation and finally by60 minutes dart plus rear spray (condensation). The setting is at 0.55W/M² at 340 nm, 1.98 kJ/hour. In the light cycle the black paneltemperature is controlled at 70±2° C. The relative humidity in the lightcycle is in the range of 50-55% and in the dark cycle 100%. Theabsorbance of the long wavelength UV band as a function of Xenon arcweathering hours are recorded

[0362] To follow the loss of UV absorbers from the clear coats, UVspectra are measured initially and after weathering at regular timeintervals. The UV spectrophotometer measures absorbance linearly up to5.5 absorbance units using a reference beam attenuation technique.

[0363] It is assumed that the degradation products from the UV absorberdo not contribute to the UV spectrum. This is tested by following theratio of absorbance of the band at about 300 nm and the band at about340 nm. The ratio does not change upon weathering the sample. Thissuggests that the UV spectrum of the weathered films correspond to theamount of UV absorber remaining in the film with very little if anycontribution to the spectrum by photo degradants.

[0364] Representative benzotriazole test compounds are incorporated intoa high solid thermoset acrylic melamine resin at a concentration of 3%by weight to give equal molar concentrations of the test benzotriazolein equal film thickness and sufficient to give a starting absorbance ofapproximately 2.0 absorbance units.

[0365] The instant benzotriazoles are especially durable in automotivecoatings as judged by low loss rates.

EXAMPLE 24 Color Change of a White Unscented Candle Wax underFluorescent Lamp Exposure

[0366] A variety of different stabilizers are evaluated in a whiteunscented candle wax under fluorescent lamp exposure. The stabilizersinclude a compound of Example 2 alone or with a hindered amine likebis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TIUVIN® 292, CIBA orbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN®123, CIBA. The ΔE values represent the change in color after exposure. Alow ΔE value indicates less change in color and is highly desired.

[0367] The instant compound alone or with the hindered amine providesexcellent protection to the white unscented candle wax fromdiscoloration.

EXAMPLE 25 Color Fade of Green Scented Candle Wax under UV Lamp Exposure

[0368] A variety of different stabilizers are evaluated in green scentedcandle wax obtained from the Candle Corporation of America under UV lampexposure at 368 nm wavelength. The stabilizers include a compound ofExample 1 alone or with a hindered amine likebis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA orbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN®123, CIBA. The ΔE values represent the change in color after exposure. Alow ΔE value indicates less change in color and is highly desired.

[0369] The instant compound alone or with the hindered amine providesexcellent protection to the green scented candle wax from dye fade.

EXAMPLE 26 Color Fade of a Blue Unscented Candle Wax under UV LampExposure

[0370] A variety of different stabilizers are evaluated in blueunscented candle wax under UV lamp exposure at 368 nm wavelength. Thestabilizers include a compound of Example 1 alone or with a hinderedamine like bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN®292, CIBA or bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,TINUVIN® 123, CIBA. The ΔE values represent the change in color afterexposure. A low ΔE value indicates less change in color and is highlydesired.

[0371] The instant compound alone or with the hindered amine providesexcellent protection to the blue unscented candle wax from dye fade.

EXAMPLE 27 Color Fade of Pink Scented Candle Wax under Fluorescent LampExposure

[0372] Different stabilizers are evaluated in pink scented candle waxobtained from the Candle-Lite Corporation under fluorescent lampexposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired. ΔE after Sample* (wt % add) 8.9 days 11.8days 22.3 days Blank (no add) 8.10 10.22 12.12 A (0.3%) 8.72 10.48 12.91F (0.3%) 6.75 6.50 8.58 C (0.15%) + D 2.07 4.37 5.94 (0.15%) A (0.15%) +B 3.18 2.20 2.79 (0.15%) E (0.15%) + B 4.21 3.24 2.13 (0.15%) F(0.15%) + G 1.77 2.49 4.16 (0.15%)

[0373] These data show that a hindered amine in combination with aninstant UV absorber protects the pink scented candle wax far better thanthe hindered amine or a UV absorber alone.

EXAMPLE 28 Color Fade of Pink Scented Candle Wax under UV Lamp Exposure

[0374] A variety of different stabilizers are evaluated in pink scentedcandle wax obtained from the Candle-Lite Corporation under UV lampexposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired. ΔE after Sample* (wt % add) 7.6 days 13.5days 36.7 days Blank (no add) 16.16 16.44 20.27 A (0.3%) 13.93 15.2015.88 F (0.3%) 14.79 16.41 17.53 C (0.15%) + D 8.93 7.72 9.62 (0.15%) F(0.15%) + G 2.99 3.72 5.59 (0.15%) A (0.15%) + B 1.54 1.67 3.08 (0.15%)E (0.15%) + B 3.19 2.76 2.10 (0.15%)

[0375] These data show that a hindered amine in combination with aninstant UV absorber protects the pink scented candle wax far better thanconventional UV absorbers or a hindered amine alone.

EXAMPLE 29 Color Fade of Gray Scented Candle Wax under Fluorescent LampExposure

[0376] A variety of different stabilizers are evaluated in gray scentedcandle wax obtained from the Candle-Lite Corporation under fluorescentlamp exposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired. ΔE after Sample* (wt % add) 4.9 days 10.9days 33.9 days Blank (no add) 9.66 11.97 16.01 A (0.3%) 9.67 10.89 11.32F (0.3%) 4.88 6.16 7.55 C (0.15%) + D 1.56 4.33 8.52 (0.15%) A (0.15%) +B 1.74 2.01 4.50 (0.15%) A (0.15%) + G 0.80 1.99 4.09 (0.15%) F(0.15%) + B 1.21 1.24 3.42 (0.15%)

[0377] These data show that a hindered amine in combination with aninstant UV absorber protects the gray scented candle wax far better thanconventional UV absorbers or a hindered amine alone.

EXAMPLE 30 Color Fade of Gray Scented Candle Wax under UV Lamp Exposure

[0378] A variety of different stabilizers are evaluated in gray scentedcandle wax obtained from the Candle-Lite Corporation under UV lampexposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired. ΔE after Sample* (wt % add) 2.8 days 8.9days 22.6 days Blank (no add) 22.20 28.98 30.07 A (0.3%) 20.83 27.3725.37 F (0.3%) 23.88 26.40 25.38 C (0.15%) + D 2.30 7.06 10.96 (0.15%) F(0.15%) + G 1.98 3.68 4.89 (0.15%) A (0.15%) + B 1.10 2.58 4.14 (0.15%)F (0.15%) + B 1.01 2.18 3.58 (0.15%)

[0379] These data show that a hindered amine in combination with aninstant UV absorber protects the gray scented candle wax far better thanconventional UV absorbers or a hindered amine alone.

EXAMPLE 31 Color Fade of White Scented Candle Wax under Fluorescent LampExposure

[0380] A variety of different stabilizers are evaluated in white scentedcandle wax obtained from the Candle-Lite Corporation under fluorescentlamp exposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired. ΔE after Sample* (wt % add) 4.0 days 14.7days 33.0 days Blank (no add) 27.56 33.74 34.68 A (0.3%) 13.31 22.2426.35 F (0.3%) 21.46 30.91 32.06 C (0.15%) + D 9.39 17.68 21.24 (0.15%)F (0.15%) + G 12.47 20.93 20.14 (0.15%) A (0.15%) + B 2.87 6.27 9.32(0.15%) E (0.15%) + B 6.05 14.00 18.32 (0.15%)

[0381] These data show that a hindered amine in combination with aninstant UV absorber protects the white scented candle wax far betterthan conventional UV absorbers or a hindered amine alone.

EXAMPLE 32 Color Fade of White Scented Candle Wax under UV Lamp Exposure

[0382] A variety of different stabilizers are evaluated in white scentedcandle wax obtained from the Candle-Lite Corporation under UV lampexposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired. ΔE after Sample* (wt % add) 5.9 days 16.6days 35.0 days Blank (no add) 42.90 45.57 45.14 A (0.3%) 34.65 36.6435.07 F (0.3%) 35.55 33.80 29.30 C (0.15%) + D 24.48 28.86 27.80 (0.15%)F (0.15%) + G 14.53 21.47 22.17 (0.15%) A (0.15%) + B 7.71 10.57 12.97(0.15%) E (0.15%) + B 9.01 14.03 15.50 (0.15%)

[0383] These data show that a hindered amine in combination with aninstant UV absorber protects the white scented candle wax far betterthan conventional UV absorbers or a hindered amine alone.

EXAMPLE 33

[0384] Spectral Properties of Substituted 5-Arylbenzotriazole UVAbsorbers of Formulas I and II

[0385] The following table shows the absorption maxima and molarextinction coefficients of a number of 2H-benzotriazole UV absorbers offormulas I and II where E₁ is α-cumyl and E₂ is tert-octyl unlessotherwise indicated. A state-of-the-art commercial benzotriazole UVabsorber,2-[2-hydroxy-3,5-di-(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole(TINUVIN® 900, CIBA) and a number of instant 5-aryl substitutedcompounds are tested. The concentrations of each of the samples areidentical, namely 20 mg/L in ethyl acetate. The absorption λ maxima ofthe instant compounds at 350 to 369 nm are red-shifted, i.e. shiftedtowards the visible relative to the commercial control, which has anabsorption X maximum at 342 nm (ε 15,500). The molar extinctioncoefficients E of the 5-aryl substituted compounds substituted instantcompounds far exceed that of the control compound at the absorption λmaxima. Absorption Maxima and Molar Extinction Coefficients ofBenzotriazole UV Absorbers R or T Hammett Compound of nm Molar ε5-Substitution Constant Control* 342 (15,500) hydrogen σ_(p) = 0.0Example 7 355 (17,745) 3-trifluorophenyl σ_(m) = +0.46 Example 11 357(19,727) 3,5-bis-CF₃phenyl σ_(m) = +0.46 Example 8 350 (21,035)2-trifluorophenyl Example 15 362 (21,506) 5-methoxyphenyl σ_(p) = −0.27Example 2 356 (23,910) 4-trifluorophenyl σ_(p) = +0.53 Example 13 358(23,981) 4-cyanophenyl σ_(p) = +0.70 Example 10 356 (25,690) phenylσ_(p) = 0.0 Example 12 361 (31,903) 1,1′-biphenyl-4-yl σ_(p) = +0.05Example 16** 369 (52,629) p-phenylenebis Example 17*** 360 (25,453)5-methoxyphenyl σ_(p) = −0.27

What is claimed is:
 1. A compound of formula I or II

wherein R is phenyl, naphthyl, biphenylyl, 9-phenanthryl or said phenyl,naphthyl, biphenylyl or 9-phenanthryl substituted by one to three alkylof 1 to 18 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, R₃S—,R₃SO—, R₃SO₂, aryl of 6 to 10 carbon atoms, perfluoroalkyl of 1 to 12carbon atoms, halogen, nitro, cyano, carboxyl, alkoxycarbonyl of 2 to 19carbon atoms, hydroxyl, alkoxy of 1 to 18 carbon atoms, aryloxy of 6 to10 carbon atoms, aralkoxy of 7 to 15 carbon atoms, vinyl, acetyl,acetamido, amino, dialkylamino of 2 to 12 carbon atoms, formyl,thioalkcoxy of 1 to 18 carbon atoms, hydroxymethyl, amino-methyl,halomethyl, sulfato, phosphato or where any two substituents form abenzo ring with the aryl moiety to which they are attached, T is adirect bond, 1,4-phenylene or said phenylene substituted by one or twoalkyl of 1 to 12 carbon atoms, R₃ is alkyl of 1 to 18 carbon atoms,phenylalkyl of 7 to 15 carbon atoms or aryl of 6 to 10 carbon atoms, E₁is hydrogen, straight or branched alkyl of 1 to 24 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or saidphenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4carbon atoms, E₂ is straight or branched alkyl chain of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by 1 to 3 alkyl of 1 to 4 carbon atoms; or E₂ is alkyl of 1 to 24carbon atoms or alkenyl of 2 to 18 carbon atoms substituted by one ormore —OH, —OCOE₃, —NH₂, —NHCOE₃ or —COOE₃, or mixtures thereof; or saidalkyl or said alkenyl interrupted by one or more —O— which can beunsubstituted or substituted by one or more —OH groups; where E₃ ishydrogen or alkyl of 1 to 24 carbon atoms, and where said alkyl isinterrupted by one or more —O— and which can be substituted by one ormore —OH or —OR₂₁ groups where R₂₁ is alkyl of 1 to 12 carbon atoms; andwith the proviso that5-phenyl-2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole isexcluded; and with the further proviso that, when E₁ is hydrogen, methylor ethyl and E₂ is methyl or ethyl, R is not phenyl.
 2. A compound offormula I according to claim 1 wherein R is phenyl, 2-naphthyl,3-biphenylyl, 4-biphenylyl, 9-phenanthryl, 2-trifluoromethylphenyl,3-tnifluoromethylphenyl, 4-trifluoromethylphenyl,3,5-ditrifluoromethylphenyl, 4-cyanophenyl, 3-methylphenyl,3-isopropylphenyl, 3-fluorophenyl, 3-chlorophenyl, 3-bromophenyl,3-iodophenyl, 3-methoxy-phenyl, 3-ethoxyphenyl, 3-benzyloxyphenyl,3-hydroxyphenyl, 3-hydroxymethylphenyl, 3-thiomethylphenyl,3-bromomethylphenyl, 3-cyanophenyl, 3-vinylphenyl, 3-acetylphenyl,3-aminophenyl, 3-acetamidophenyl, 3-formylphenyl, 3-isothiocyanophenyl,2-ethylphenyl, 2-cyanophenyl, 2-acetylphenyl, 2-bromomethylphenyl,2-bromophenyl, 2-vinylphenyl, 2-aminophenyl, 2-hydroxyphenyl,2-ethoxyphenyl, 2-fluorophenyl, 2-chlorophenyl, 2-methoxyphenyl,2-formylphenyl, 2-methylphenyl, 4-n-butylphenyl, 4-n-nonylphenyl,4-methoxycarbonylphenyl, 4-cyanomethylphenyl, 4-aminomethylphenyl,4-isobutylphenyl, 4-iodophenyl, 4-thioethylphenyl, 4-bromomethylphenyl,4-benzyloxyphenyl, 4-acetylphenyl, 4-dimethylaminophenyl,4-hydroxyphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-amino-phenyl,4-n-amylphenyl, 4-ethylphenyl, 4-hydroxymethylphenyl, 4-ethoxyphenyl,4-vinylphenyl, 4-formylphenyl, 4-carboxyphenyl, 4-thiomethylphenyl,4-phenoxyphenyl, 4-methoxy-phenyl, 4-methylphenyl, 4-chlorophenyl,4-fluorophenyl, 4-bromophenyl, 2,6-dimethylphenyl, 3,5-dichlorophenyl,3,5-dimethylphenyl, 3,5-dibromophenyl, 3,5-difluorophenyl,3-chloro-4-fluorophenyl, 3,4-difluorophenyl, 3-amino-4-methylphenyl,3,4-dichlorophenyl, 3-hydroxy-4-methylphenyl, 3-amino-4-methylphenyl,3-fluoro-4-bromophenyl or 3-fluoro-4-formyl-phenyl, and where E₁ and E₂are independently straight or branched chain alkyl of 4 to 24 carbonatoms or phenylalkyl of 7 to 15 carbon atoms, or E₁ is additionallyphenyl.
 3. A compound of formula II according to claim 1 where T is adirect bond, 1,4-phenylene or 2,5-di-n-hexyl-1,4-phenyene and where E₁and E₂ are independently a straight or branched chain alkyl of 4 to 24carbon atoms or phenylalkyl of 7 to 15 carbon atoms.
 4. A compound offormula I or II according to claim 1 where R is phenyl,2-trifluoromethylphenyl, 3-trifluoromethylphenyl,4-trifluoromethylphenyl, 3,5-di-trifluoromethylphenyl, 4-cyanophenyl,4-methoxyphenyl or 1,1′biphenyl-4-ylphenyl, T is 1,4-phenylene, E₁ isphenyl or α-cumyl, and E₂ is tert-butyl or tert-octyl.
 5. A compound offormula I according to claim 4 where R is phenyl or4-trifluoromethylphenyl; E₁ is α-cumyl; and E₂ is tert-octyl.
 6. Aprocess for the preparation of a compound of formula I or II

where R, T, E₁ and E₂ are as defined above, by the reaction of anarylboronic acid or ester of formula III or IV R—B(OR₁)(OR₂)  (11)(R₂O)(R₁O)B-T-B(OR₁)(OR₂)  (IV) where R₁ and R₂ are independentlyhydrogen, alkyl of 1 to 12 carbon atoms, or R₁ and R₂ together arealkylene of 2 to 4 carbon atoms; with a 5-substituted benzotriazole offormula V

where X is chloro, bromo or iodo, or tosylate, in the presence of aneffective amount of a palladium (II) catalyst at a temperature betweem10 to 100° C.
 7. A process according to claim 6 wherein X is bromo.
 8. Aprocess according to claim 6 wherein the reaction is carried out at atemperature between 50 to 95° C.
 9. A process according to claim 6wherein the amount of palladium (II) catalyst is 0.01 to 10 mol percent.10. A process according to claim 6 wherein additionally a ligand ispresent.
 11. A process according to claim 10 wherein the ligand istriphenylphosphine, 2-(di-tert-butylphosphino)biphenyl,1,1′-bis[2,4,8,10-tetrakis(tert-butyl)-dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]ferrocene,tris(2,4-di-tert-butylphenyl) phosphite or2,2′,2″-nitrilo[trietbyl-tris(3,3′,5,5′-tetra-tert-butyl-1,1′biphenyl-2,2′-diyl)phosphite].12. A process according to claim 11 wherein the ligand istriphenylphosphine.
 13. A process according to claim 6 wherein theprocess is an anhydrous process with dioxane as solvent and potassiumfluoride as a base.
 14. A process according to claim 6 wherein theprocess is carried out using n-propanol or isopropanol as solvent with asmall amount of water present and aqueous sodium carbonate as base. 15.A composition stabilized against thermal, oxidative or light-induceddegradation which comprises, (a) an organic material subject to thermal,oxidative or light-induced degradation, and (b) an effective stabilizingamount of a compound of formula I or II

wherein R is phenyl, naphthyl, biphenylyl, 9-phenanthryl or said phenyl,naphthyl, biphenylyl or 9-phenanthryl substituted by one to three alkylof 1 to 18 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, R₃S—,R₃SO—, R₃SO₂, aryl of 6 to 10 carbon atoms, periluoroalkyl of 1 to 12carbon atoms, halogen, nitro, cyano, carboxyl, alkoxycarbonyl of 2 to 19carbon atoms, hydroxyl, alkoxy of 1 to 18 carbon atoms, aryloxy of 6 to10 carbon atoms, aralkoxy of 7 to 15 carbon atoms, vinyl, acetyl,acetamido, amino, dialkylamino of 2 to 12 carbon atoms, formyl,thioalkoxy of 1 to 18 carbon atoms, hydroxymethyl, amino-methyl,halomethyl, sulfato, phosphato or where any two substituents form abenzo ring with the aryl moiety to which they are attached, T is adirect bond, 1,4-phenylene or said phenylene substituted by one or twoalkyl of 1 to 12 carbon atoms, R₃ is alkyl of 1 to 18 carbon atoms,phenylalkyl of 7 to 15 carbon atoms or aryl of 6 to 10 carbon atoms, E₁is hydrogen, straight or branched alkyl of 1 to 24 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or saidphenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4carbon atoms, E₂ is straight or branched alkyl chain of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by 1 to 3 alkyl of 1 to 4 carbon atoms; orE₂ is alkyl of 1 to 24carbon atoms or alkenyl of 2 to 18 carbon atoms substituted by one ormore —OH, —OCOE₃, —NH₂, —NHCOE₃ or —COOE₃, or mixtures thereof; or saidalkyl or said alkenyl interrupted by one or more —O— which can beunsubstituted or substituted by one or more —OH groups; where E₃ ishydrogen or alkyl of 1 to 24 carbon atoms, and where said alkyl isinterrupted by one or more —O— and which can be substituted by one ormore —OH or —OR₂₁ groups where R₂₁ is alkyl of 1 to 12 carbon atoms. 16.A composition according to claim 15 wherein component (a) is athermoplastic polyolefin, polyester, polyester urethane, polyetherurethane or a water-borne coating.
 17. A composition according to claim15 wherein component (a) is selected from the group consisting ofpolypropylene, thermoplastic polyolefin, low density polyethylene,medium density polyethylene, high density polyethylene, linear lowdensity polyethylene, poly(butene-1), ethylene/vinyl acetate copolymer,ethylene/propylene copolymer, copolymers of ethylene or propylene withother alpha-olefins, copolymers of acrylonitrile-butadiene-styrene(ABS), copolymers of acrylonitrile and styrene that are impact modifiedwith ethylene-propylene rubber or ethylene/propylene/alpha-olefin rubberor butyl acrylate rubber, blends of ABS and polycarbonate, blends of ABSand poly(vinyl chloride) (PVC), poly(vinyl chloride), copolymers ofstyrene and butadiene (HIPS), copolymers of styrene and butadiene thatalso contain ethylene-propylene rubber orethylene/propylene/alpha-olefin rubber or butyl acrylate rubber,thermoplastic elastomers and thermoplastic vulcanizates.
 18. Acomposition according to claim 15 wherein component (a) is a polyesteror polyether urethane or water-borne coating.
 19. A compositionaccording to claim 15 which additionally contains an effectivestabilizing amount of at least one coadditive stabilizer selected fromthe group consisting of the phenolic antioxidants, metal stearates,metal oxides, organophosphorus compounds, furanone antioxidants,hydroxylamines, UV absorbers, non-NOR hindered amines, NOR hinderedamines and mixtures thereof.
 20. A composition according to claim 15which is a stabilized stoving lacquer wherein component (a) is an acidcatalyzed resin based on hot crosslinkable, acrylic, acrylic melamine,polyester, polyurethane, polyamide or alkyd resin.
 21. A compositionaccording to claim 15 which additionally contains a UV absorber selectedfrom the group consisting of the benzotriazoles, the s-triazines, theoxanilides, the salicylates, the hydroxybenzophenones, the benzoates andthe α-cyanoacrylates.
 22. A composition according to claim 15 which isan enamel of high solids content for industrial finishes.
 23. Acomposition according to claim 15 which is a finishing enamel forautomobiles.
 24. A composition according to claim 15 wherein component(a) is a polyolefin, polycarbonate, a styrenic, ABS, a nylon(polyamide), a polyester, a polyurethane, a polyacrylate, a rubbermodified styrenic, poly(vinyl chloride), poly(vinyl butyral), polyacetal(polyoxymethylene), or other blends or copolymers such aspoly(ethylene/1,4-cyclohexylenedimethylene terephthalate) PETG or anethylene/acrylic acid copolymer or salts thereof (an ionomer).
 25. Acomposition according to claim 24 wherein the polymer is a polyester ora polyacrylate.
 26. A composition according to claim 24 wherein thepolyester is poly(ethylene terephthalate), poly(butylene terephthalate)or poly(ethylene naphthalenedicarboxylate), or copolymerpoly(ethylene/1,4-cyclohexylenedimethylene terephthalate) PETG.
 27. Acomposition according to claim 15 wherein component (a) is a polyolefinor polycarbonate.
 28. A composition according to claim 15 whereincomponent (a) is a photographic composition.
 29. A composition accordingto claim 15 wherein the organic material is a candle wax.
 30. Acomposition according to claim 29 wherein the candle wax additionallycontains an effective stabilizing amount of a hindered amine.
 31. Acompound which is 5-bromio-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl)2H-benzotriazole.